CN108517190A - A kind of acrylic acid glue for tile and its application - Google Patents
A kind of acrylic acid glue for tile and its application Download PDFInfo
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- CN108517190A CN108517190A CN201810371172.8A CN201810371172A CN108517190A CN 108517190 A CN108517190 A CN 108517190A CN 201810371172 A CN201810371172 A CN 201810371172A CN 108517190 A CN108517190 A CN 108517190A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/003—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/10—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of amides or imides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
- E04F13/00—Coverings or linings, e.g. for walls or ceilings
- E04F13/07—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor
- E04F13/08—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of a plurality of similar covering or lining elements
- E04F13/0885—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of a plurality of similar covering or lining elements specially adapted for being adhesively fixed to the wall; Fastening means therefor; Fixing by means of plastics materials hardening after application
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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Abstract
The present invention relates to adhesive areas, and in particular to arrives a kind of acrylic acid glue for tile and its application.The acrylic acid glue for tile, in parts by weight, including acrylate copolymer mother liquor 40~50, bleeding agent 0.1~1.5, water 50~65；The bleeding agent is sulfonation esters bleeding agent.
Description
Technical field
The present invention relates to adhesive areas, and in particular to arrives a kind of acrylic acid glue for tile and its application.
Background technology
Ceramic tile has a wide range of applications in decorative material for wall surface, and ceramic tile is with the metal oxide of fire resisting and semimetal oxygen
Compound, via grinding, mixing, compacting, glazing, sintering process and the building such as the porcelain of a kind of acid and alkali-resistance formed or stone matter or
Ornament materials, raw material are mostly mixed by clay, quartz sand etc..
It pastes ceramic tile and generally uses cement mortar or this traditional mode of cement mortar in China.But use this traditional side
Method often has many drawbacks.If binder smearing is irregular, ceramic tile is easy to happen hollowing, falls off；The caking property of common bond
Difference, bulk ceramic tile or the stone material etc. being attached to above must be mechanically fixed or be reinforced, and also not have anti-slipping property.So ceramic tile
It must be pasted since bottom, and need to use locator between ceramic tile and ceramic tile, to ensure that the ceramic tile after pasting is horizontal flat
Vertically, surfacing.It can be seen that such method takes very much, efficiency is low, material utilization amount is big, and to worker's construction technology
Level requirement is high, and due to being limited by this kind of material self performance, construction quality is difficult to ensure.
Ceramic tile adhesive is a kind of using cement as the high-quality adhesive by polymer modification of substrate, has flexibility and rapid-curing cutback
Property, thickness construction is all suitable, and special formula can paste ceramic tile on various types of base materials.Consisting of cement, stone
Sand and concentration tackifier, the sticker compared to the prior art, have boundary of works area is wide, adhesion strength is strong, easy for construction, ceramic tile
Do not have to the features such as water-soaked, firm time are long, and there are sufficient adjustment times to construction personnel before construction with wall, ground,
Thus, it has good value for applications.Ceramic tile adhesive can make up the defect of cement and general polymer mortar, because
Its water proofing property, caking property and durability are good, overcome facing existing for ordinary cement, waterproof mortar or common wall and floor tile adhesive agent
Brick bond loosely, hollowing, crack, fall off, seeping water, the drawbacks such as performance is unstable, from architectural exterior-protecting construction waterproofing plaster coat to building
Bonding, the waterproof of finishing material all show superior function.It is theoretical according to " organic-inorganic object ", is mixed by best polymer
Amount mixing, the materials such as stringent control polymer mix ratio.Characteristic with inorganic cement, and have the high caking ability of organic gel
Feature, collection waterproof are bonded in one.It is to substitute conventional cement and general polymer mortar, modern medium-to-high grade building is optimal
Water-proof bond material.
CN103011731A discloses a kind of tile paste and the dual-purpose adhesive of joint filling, group be divided into cement, filler, can be again
Dispersed latex powder, cellulose ether, early strength agent, thixotropic lubricant, lignocellulosic, hydrophober, anti-accumulation of salt in the surface soil agent, mould inhibitor, dispersion
Agent.Its disclosed dual-purpose adhesive is to need to prepare different adhesive respectively for the stickup and joint filling of existing ceramic tile, due to
Stickup adhesive and the adhesive products of joint filling formula are different, and dispensing can cause the repetition in working hour, waste material respectively
Problem, provide it is a kind of can paste, the adhesive that joint filling is dual-purpose, but from its record components by weight formula from the point of view of,
Cement accounts for 20-40%, and filler accounts for 50-70%, it can be seen that this dual-purpose adhesive is still to belong to cement-based adhesive, is being applied
It is possible to the problems such as ceramic tile caused by there is the strong basicity due to hydrolysis product of cement aoxidizes when to tile paste and joint filling, and is filled out
Expect preferred quartz sand, beautiful decorative effect can not be played when as pointing for coarse aggregate.In addition, traditional ceramic tile is viscous
Knot agent is when stirring at the scene, and the mode of thick-layer construction not only matches unstable, but also can cause larger pollution to environment, construct
Speed is slow, time-consuming and laborious, can also cause the waste of material, and cohesive force is weak, durability is poor, is easy to peel off.Construction efficiency and
It pastes safety and does not obtain actual raising.
Invention content
In order to solve the above-mentioned technical problem, the first aspect of the present invention provides a kind of acrylic acid glue for tile, the propylene
Sour glue for tile, in parts by weight, including acrylate copolymer mother liquor 40~50, bleeding agent 0.1~1.5, water 50~65；It is described
Bleeding agent is sulfonation esters bleeding agent.
As a kind of perferred technical scheme, the preparation method of the acrylate copolymer mother liquor includes the following steps：
(1) emulsifier I is stirred with deionized water, is configured to emulsifier aqueous solution, nuclear layer monomer is added dropwise, at room temperature
Stirring 30~45min of pre-emulsification obtains nuclear layer monomer lotion；Emulsifier II is stirred with deionized water, is configured to emulsifier
Shell monomers are added dropwise in aqueous solution, stir 30~45min of pre-emulsification at room temperature and obtain shell monomers lotion；
(2) initiator and nuclear layer monomer lotion is added dropwise under conditions of being passed through nitrogen and stirring, is then warming up to system
It 75~85 DEG C, is stirred to react, continues 45~60min of stirring after occurring blue-fluorescence in system, stop reaction to get seed breast
Liquid；
(3) seed emulsion obtained by (2) step is cooled to 30~40 DEG C, initiator, sodium carbonate and residue is at the uniform velocity added dropwise
Nuclear layer monomer lotion, then system be warming up to 80 DEG C, 30~45min of insulation reaction, propylene acid for adjusting pH value is added to 4~5,
30~45min is stirred, then adjusting pH value to 7~8 obtains stratum nucleare polymer emulsion；
(4) and then in stratum nucleare polymer emulsion initiator is added, stirs 10~15min, emulsifier is then added dropwise successively
III, the shell monomers lotion and sodium bicarbonate, then system be warming up to 90 DEG C, insulation reaction 1~1.5 hour；
Propylene acid for adjusting pH value is added in system obtained by (5) (4) steps to 4~5, is stirred to react 45~60min, then
The toluene solution that rosin is added stirs 15min, and system temperature is down to room temperature discharging to get the acrylate copolymer mother liquor.
As a kind of perferred technical scheme, the nuclear layer monomer includes acrylamide and acrylic ester monomer；It is described
Acrylic ester monomer is selected from (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl)
Isobutyl acrylate, Isooctyl acrylate monomer, (methyl) acrylic acid, (methyl) glycidyl acrylate, (methyl) acrylic acid hydroxyl
Ethyl ester, it is one or more in (methyl) hydroxypropyl acrylate.
As a kind of perferred technical scheme, the shell monomers include vinylidene, methylpropene sodium sulfonate, styrene
And Isobutyl methacrylate, weight ratio 1：(0.1~0.3)：(0.2~0.5)：(0.2~0.5).
As a kind of perferred technical scheme, the shell monomers include vinylidene, methylpropene sodium sulfonate, styrene
And Isobutyl methacrylate, weight ratio 1：0.2：0.35：0.35.
As a kind of perferred technical scheme, the emulsifier I is the mixture of anion emulsifier and non-ionic emulsifier；
The weight ratio of the anion emulsifier and nonionic emulsifier is 1：(3~5).
As a kind of perferred technical scheme, the emulsifier II is by disproportionation rosin acid potassium, potassium oleate and polyoxyethylene nonyl phenyl
Vinyl ethers forms, and weight ratio is (1.5~2)：(0.8~1.5)：1.
As a kind of perferred technical scheme, the glass transition temperature of gained raw material after the acrylic acid glue for tile is dried
It is -45~-35 DEG C.
As a kind of perferred technical scheme, the decomposition temperature of gained raw material is 430 after the acrylic acid glue for tile drying
~450 DEG C.
The second aspect of the invention provides the application of above-mentioned acrylic acid glue for tile, is applied to the stickup of ceramic tile.
Advantageous effect：Acrylic acid glue for tile provided by the present application be emulsion state, patch block using when can directly be applied to porcelain
The brick back side uses after also can directly being mixed with water after pouring into cement use and stirring evenly, easy to use, while the liquid of the present invention
Body glue for tile does not play dirt, pollution-free to construction personnel and construction environment close friend；Acrylic acid glue for tile provided by the present application have compared with
High adhesion strength, adhesive force etc. are not easy hollowing in application process, and the time of patch block is also substantially reduced, and are conducive to improve and apply
Work efficiency rate and workability；Acrylic acid glue for tile provided by the present application has good stability, as high-temperature stability, machinery are steady
Qualitative and freeze-thaw stability, can be under the environment such as high temperature or low temperature, and it is permanent especially to be stored under ultra-low temperature surroundings, and
Its comprehensive performance is not affected substantially when being used after thawing, in addition, after acrylic acid glue for tile use provided by the present application
It is long-term to work with good water resistance.
Description of the drawings
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
Obtain other attached drawings according to these attached drawings.
Fig. 1 is the infrared spectrum for the acrylic acid glue for tile that embodiment 3 provides；
Fig. 2 is the infrared spectrum that the acrylic acid glue for tile that embodiment 3 provides dries sample；
Fig. 3 is the hydrogen nuclear magnetic resonance spectrogram that the acrylic acid glue for tile that embodiment 3 provides dries sample；
Fig. 4 is thermogravimetric analysis (TGA) figure that the acrylic acid glue for tile that embodiment 3 provides dries sample；
Fig. 5 is differential scanning calorimetry (DSC) figure that the acrylic acid glue for tile that embodiment 3 provides dries sample.
Specific implementation mode
The detailed description for preferred implementation method of the invention below of participating in the election of and including embodiment this hair can be more easily understood
Bright content.Unless otherwise defined, all technologies used herein and scientific terminology have common with fields of the present invention
The normally understood identical meaning of technical staff.When there is a conflict, the definition in this specification shall prevail.
As used herein term " by ... prepare " it is synonymous with "comprising".Term "comprising" used herein, " comprising ",
" having ", " containing " or its any other deformation, it is intended that cover non-exclusionism includes.For example, the combination comprising listed elements
Object, step, method, product or device are not necessarily limited to those elements, but may include not expressly listed other elements or
Such composition, step, method, product or the intrinsic element of device.
Conjunction " Consists of " excludes any element that do not point out, step or component.If in claim, this
Phrase will make claim be closed, so that it is not included the material in addition to the material of those descriptions, but relative normal
Except rule impurity.When being rather than immediately following after theme in the clause that phrase " Consists of " appears in claim main body,
It is only limited to the element described in the clause；Other elements are not excluded except the claim as a whole.
Equivalent, concentration or other values or parameter are excellent with range, preferred scope or a series of upper limit preferred values and lower limit
When the Range Representation that choosing value limits, this, which should be understood as, specifically discloses by any range limit or preferred value and any range
Any pairing of lower limit or preferred value is formed by all ranges, regardless of whether the range separately discloses.For example, when open
When range " 1 to 5 ", described range should be interpreted as including range " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to
5 ", " 1 to 3 and 5 " etc..When numberical range is described herein, unless otherwise stated, otherwise range intention includes its end
Value and all integers and score in the range.
Singulative includes that plural number discusses object, unless the context clearly dictates otherwise." optional " or it is " arbitrary
It is a kind of " refer to that the item described thereafter or event may or may not occur, and the description include situation that event occurs and
The situation that event does not occur.
Approximate term in specification and claims is used for modifying quantity, and it is specific to indicate that the present invention is not limited to this
Quantity further includes the modified part of the acceptable change without lead to related basic function close to the quantity.Phase
It answers, modifies a numerical value with " about ", " about " etc., mean that the present invention is not limited to the exact numericals.In some examples, approximate
Term likely corresponds to the precision of the instrument of measured value.In present specification and claims, range limits can be with
Combination and/or exchange, these ranges include all subranges contained therebetween if not stated otherwise.
The terms such as (methyl) methyl acrylate occurred in claim and specification refer to methyl methacrylate or third
E pioic acid methyl ester, including two kinds of possible situations.In addition, the examination of infrared spectrum, nuclear magnetic resonance test, DSC in the application and TGA
Equal tests are tested according to conventional operating method.
In addition, indefinite article "an" before element of the present invention or component and "one" quantitative requirement to element or component
(i.e. occurrence number) unrestriction.Therefore "one" or "an" should be read as including one or at least one, and odd number
The element or component of form also include plural form, unless the apparent purport of the quantity refers to singulative.
In order to solve the above-mentioned technical problem, the first aspect of the present invention provides a kind of acrylic acid glue for tile, the propylene
Sour glue for tile, in parts by weight, including acrylate copolymer mother liquor 40~50, bleeding agent 0.1~1.5, water 50~65；It is described
Bleeding agent is sulfonation esters bleeding agent.
In a preferred embodiment, the acrylic acid glue for tile, in parts by weight, including acrylate copolymer
Mother liquor 41~42, bleeding agent 0.5~1.0, water 57~58.
Bleeding agent is amphipathic using its strand, improves the affinity of acrylic acid glue for tile and ceramic tile surface and metope,
Promote glue for tile toward the infiltration sprawled on object surface is sticked, improves the bonding force between glue for tile and base material.The infiltration of the present invention
It refers to being obtained after esterification by carboxylic acid and alcohol compound that agent, which uses sulfonation esters bleeding agent, the sulfonation esters bleeding agent,
The product arrived, using the compound obtained by sulfonating reaction.In a preferred embodiment, the bleeding agent selects sulfo group
Dioctyl succinate sodium salt.
In a preferred embodiment, the preparation method of the acrylate copolymer mother liquor includes the following steps：
(1) emulsifier I is stirred with deionized water, is configured to emulsifier aqueous solution, nuclear layer monomer is added dropwise, at room temperature
Stirring 30~45min of pre-emulsification obtains nuclear layer monomer lotion；Emulsifier II is stirred with deionized water, is configured to emulsifier
Shell monomers are added dropwise in aqueous solution, stir 30~45min of pre-emulsification at room temperature and obtain shell monomers lotion；
(2) initiator and nuclear layer monomer lotion is added dropwise under conditions of being passed through nitrogen and stirring, is then warming up to system
It 75~85 DEG C, is stirred to react, continues 45~60min of stirring after occurring blue-fluorescence in system, stop reaction to get seed breast
Liquid；
(3) seed emulsion obtained by (2) step is cooled to 30~40 DEG C, initiator, sodium carbonate and residue is at the uniform velocity added dropwise
Nuclear layer monomer lotion, then system be warming up to 80 DEG C, 30~45min of insulation reaction, propylene acid for adjusting pH value is added to 4~5,
30~45min is stirred, then adjusting pH value to 7~8 obtains stratum nucleare polymer emulsion；
(4) and then in stratum nucleare polymer emulsion initiator is added, stirs 10~15min, emulsifier is then added dropwise successively
III, the shell monomers lotion and sodium bicarbonate, then system be warming up to 90 DEG C, insulation reaction 1~1.5 hour；
Propylene acid for adjusting pH value is added in system obtained by (5) (4) steps to 4~5, is stirred to react 45~60min, then
The toluene solution that rosin is added stirs 15min, and system temperature is down to room temperature discharging to get the acrylate copolymer mother liquor.
In a preferred embodiment, the nuclear layer monomer includes acrylamide and acrylic ester monomer；It is preferred that
, weight ratio 1：(1~2.2)；
The acrylic ester monomer is selected from (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid
N-butyl, (methyl) isobutyl acrylate, Isooctyl acrylate monomer, (methyl) acrylic acid, (methyl) glycidyl acrylate,
(methyl) hydroxy-ethyl acrylate, it is one or more in (methyl) hydroxypropyl acrylate；Preferably, the acrylic ester monomer
For the mixture of Isooctyl acrylate monomer and methyl methacrylate；Preferably, the Isooctyl acrylate monomer and methyl methacrylate
The weight ratio of ester is (1.2~1.8)：1.
Nuclear layer monomer selects acrylamide to utilize the pole of amido bond in acrylamide with the monomer of esters of acrylic acid compounding
Property, it improves glue for tile and is sticked the affinity and adhesiveness of object, while can also utilize in amido bond and system between hydrone
Water and effect prevent hydrone ordered arrangement at low temperature, destroy the crystal seed of generation, avoid lotion because unstable under low temperature
Determine and flocculating setting.In addition, using the soft monomer (such as Isooctyl acrylate monomer) of different proportion and hard list in stratum nucleare polymerized emulsion
Body (such as methyl methacrylate), also with good adhesion strength while making the glue for tile of gained with good stability
Etc. mechanical performances.
In a preferred embodiment, the shell monomers include vinylidene, methylpropene sodium sulfonate, styrene
And Isobutyl methacrylate, weight ratio 1：(0.1~0.3)：(0.2~0.5)：(0.2~0.5)；Preferably, institute
It includes vinylidene, methylpropene sodium sulfonate, styrene and Isobutyl methacrylate, weight ratio 1 to state shell monomers：
0.2：0.35：0.35.
Shell monomers select the said components of different proportion, and gained lotion is improved using the synergistic effect between different component
Stability and comprehensive performance.It is different using the vinylidene of different proportion, methylpropene sodium sulfonate, styrene and methacrylic acid
Gumminess obtained by butyl ester is moderate, and the surface tension of lotion is smaller, is easy to sprawl and soak in substrate surface in use,
So that the caking property between the lotion and base material gets a promotion.Simultaneously in the polar group (such as sulfonate radical) and system in these components
Moisture interaction, increase polymer and water and active force, improve its stability.In addition, being used in sheath polymers lotion
The soft monomer (such as Isobutyl methacrylate) and hard monomer (such as styrene) of different proportion are so that the glue for tile of gained has very
Also there are the mechanical performances such as good adhesion strength while the stability got well.
In a preferred embodiment, the emulsifier I is the mixture of anion emulsifier and non-ionic emulsifier；
The weight ratio of the anion emulsifier and nonionic emulsifier is 1：(3~5)；Preferably, the anion emulsifier and
The weight ratio of nonionic emulsifier is 1：3.5.
The anion emulsifier refers to after dissolving in water, and the surface that active part tendency is dissociated into negative ion is lived
Property substance, feature shows as tool there are one big organic anion.The anion emulsifier can be selected from dodecyl sulphur
Sour sodium, benzene sulfonic acid sodium salt, sodium methanesulfonate, acid dimethyl sodium, isopropyl sodium sulfonate, enuatrol, sodium laurate, sodium naphthenate,
Neopelex, odium stearate etc.；Preferably, the anion emulsifier selects lauryl sodium sulfate.
The nonionic emulsifier refers to unionization in aqueous solution, the surfactant with hydrophilic lipophilic group,
Lipophilic group in molecule is roughly the same with the lipophilic group of ionic surfactant, and hydrophilic radical is mainly by having one
The oxygen-containing group (such as hydroxyl and polyoxyethylene chain) of fixed number amount is constituted.The nonionic emulsifier can select polyoxyethylene ether
Class nonionic emulsifier；Preferably, the nonionic emulsifier is nonylphenol polyoxyethylene ether.
In a preferred embodiment, the emulsifier II is by disproportionation rosin acid potassium, potassium oleate and polyoxyethylene nonyl phenyl
Vinyl ethers forms, and weight ratio is (1.5~2)：(0.8~1.5)：1；Preferably, weight ratio is 1.8：1.2：1.
The disproportionation rosin acid potassium is in the presence of a catalyst, to borrow a part for potassium rosinate under the action of inorganic acid and heat
It is aoxidized, another part is reduced the product of gained, contains dehydroabietic acid potassium, dihydro potassium rosinate, tetrahydrogenated rosin acid potassium etc.
Component.
Emulsifier II is improved single using disproportionation rosin acid potassium, potassium oleate and the Nonyl pheno base ether of different proportion
Body is in the course of the polymerization process and resulting polymers emulsion intercalation method.Disproportionation rosin acid potassium have big cyclic structure, rigidity compared with
Greatly, the micella formed during the reaction is thicker, but since its flexibility is small, the intensity of micella is weaker, and disproportionation rosin acid potassium
It is mutually compounded with the emulsifier of this long-chain of potassium oleate, the long chain of potassium oleate is made to be interspersed in the formation of disproportionation rosin acid potassium at random
In micella, the intensity and stability of micella are improved.It recycles nonionic emulsifier to form one layer in this micellar surface simultaneously to glue
Attached layer keeps micellar surface more smooth, reduces the roughness of micellar surface, avoids reunion flocculation between micella, improves lotion
Stability.
In a preferred embodiment, the emulsifier III is reactable emulsifier；The reactable emulsification
Agent is the reactive emulsifier containing allyl or vinyl；It is preferred that using sodium vinyl sulfonate, 2- allyl ether -3- hydroxyls third
It is one or more in alkane -1- sodium sulfonates, alkyl phenol allyl polyether sodium sulphate.
A certain amount of reactable emulsification is added before stratum nucleare polymer emulsion surface aggregate forms sheath polymers lotion
Agent, can form a certain amount of core-shell graft copolymer between stratum nucleare and shell while increasing micella, then with shell monomers phase
Effect improves the interaction between stratum nucleare and shell, improves the tensile bond strength and stability of gained lotion.In addition, reaction
In the process, add pre-emulsified shell monomers when preparing sheath polymers lotion, the generation of micella in control system, obtain compared with
The formation of uniform nucleocapsid.
In the present invention, the initiator is persulfate initiator, can be exemplified as：Ammonium persulfate, sodium peroxydisulfate and over cure
Sour potassium.
In a preferred embodiment, the initiator is ammonium persulfate.
A certain amount of sodium carbonate is added when seed emulsion surface aggregate forms stratum nucleare polymer emulsion, then with propylene
Acid for adjusting pH value reacts away sodium carbonate in stratum nucleare polymer particle, so that stratum nucleare particle surface is formed a certain amount of hole, similarly
A certain amount of sodium bicarbonate is also added when preparing sheath polymers lotion, obtains polymer particle surface and inside all has not
The active force between hydrone in polymer and system is improved in regular distribution, the different hole of pore size, reinforces gathering low also lower
Water and the effect for closing object improve stability and freeze-thaw stability under low temperature.
In a preferred embodiment, the glass transition temperature of gained raw material after the acrylic acid glue for tile is dried
It is -45~-35 DEG C.
The glass transition temperature is obtained using resistance to board differential scanning calorimeter (DSC) test of speeding of Germany, and test is used
Sample quality is 5.0~10.0mg, and test heating rate is 20 DEG C/min.Glass transition temperature herein refer to after sample is heated by
When glassy transition is viscous state or elastomeric state, inflection temperature when changing on DSC curve.
In a preferred embodiment, the decomposition temperature of gained raw material is 430 after the acrylic acid glue for tile drying
~450 DEG C.
The decomposition temperature is obtained using U.S. TA boards thermogravimetric analyzer (TGA) test, the heating rate in test process
For 20 DEG C/min.Decomposition temperature herein refers to temperature of the sample when weight loss rate is most fast on TGA curves, is also to TGA
Curve takes the peak temperature on the curve obtained by differential.
The second aspect of the invention provides the application of above-mentioned acrylic acid glue for tile, is applied to the stickup of ceramic tile.
The present invention is specifically described below by embodiment.It is necessarily pointed out that following embodiment is only used
In the invention will be further described, it should not be understood as limiting the scope of the invention, professional and technical personnel in the field
Some the nonessential modifications and adaptations made according to the content of aforementioned present invention, still fall within protection scope of the present invention.
In addition, if without other explanations, it is raw materials used to be all commercially available, it is purchased from traditional Chinese medicines chemical reagent.
Embodiment
Embodiment 1
Embodiment 1 provides a kind of acrylic acid glue for tile, the acrylic acid glue for tile, in parts by weight, including acrylic acid
Ester copolymer mother liquor 40, bleeding agent 0.1, water 50；The bleeding agent is sodium dioctyl sulfosuccinate.
The preparation method of the acrylate copolymer mother liquor includes the following steps：
(1) 0.2g emulsifiers I and 15ml deionized waters are stirred, are configured to emulsifier aqueous solution, 19.0g cores are added dropwise
Layer monomer stirs pre-emulsification 30min and obtains nuclear layer monomer lotion at room temperature；0.22g emulsifiers II and 10ml deionized waters are stirred
Mixing is mixed, emulsifier aqueous solution is configured to, 12.3g shell monomers are added dropwise, pre-emulsification 30min is stirred at room temperature and obtains shell monomers
Lotion；
(2) 0.2g initiators are added dropwise under conditions of being passed through nitrogen and stirring and (0.2g initiators are dissolved in 8ml deionizations
It is added dropwise after in water) and 6ml nuclear layer monomer lotions, system is then warming up to 75 DEG C, is stirred to react, it is glimmering to occur blue in system
Continue to stir 45min after light, stops reaction to get seed emulsion；
(3) seed emulsion obtained by (2) step is cooled to 30 DEG C, 0.04g initiators, 1.2g sodium carbonate is at the uniform velocity added dropwise
With 9ml nuclear layer monomer lotions, then system be warming up to 80 DEG C, insulation reaction 30min, propylene acid for adjusting pH value is added to 4, stirring
Then 30min adjusts pH value and obtains stratum nucleare polymer emulsion to 7；
(4) and then in stratum nucleare polymer emulsion 0.04g initiators are added, stirs 10min, 0.06g is then added dropwise successively
Emulsifier III, the shell monomers lotion and 0.08g sodium bicarbonates, then system be warming up to 90 DEG C, insulation reaction 1 hour；
Propylene acid for adjusting pH value is added in system obtained by (5) (4) steps to 5, is stirred to react 45min, 4ml pines are then added
(rosin is 1 with toluene mass ratio to fragrant toluene solution：1.2) 15min is stirred, system temperature is down to room temperature discharging to get described
Acrylate copolymer mother liquor.
The emulsifier I is the mixture of lauryl sodium sulfate and Nonyl pheno base ether, and weight ratio is
1：3；The emulsifier II is made of disproportionation rosin acid potassium, potassium oleate and Nonyl pheno base ether, and weight ratio is
1.5：0.8：1；The emulsifier III is sodium vinyl sulfonate；The initiator is ammonium persulfate；The nuclear layer monomer is propylene
The mixture of amide, methyl methacrylate and Isooctyl acrylate monomer, weight ratio 1：0.4：0.6；The shell monomers
For the mixture of vinylidene, methylpropene sodium sulfonate, styrene and Isobutyl methacrylate, weight ratio 1：0.1：
0.2：0.2.
Embodiment 2
Embodiment 2 provides a kind of acrylic acid glue for tile, the acrylic acid glue for tile, in parts by weight, including acrylic acid
Ester copolymer mother liquor 50, bleeding agent 1.5, water 65；The bleeding agent is sodium dioctyl sulfosuccinate.
The preparation method of the acrylate copolymer mother liquor includes the following steps：
(1) 0.2g emulsifiers I and 15ml deionized waters are stirred, are configured to emulsifier aqueous solution, 19.0g cores are added dropwise
Layer monomer stirs pre-emulsification 45min and obtains nuclear layer monomer lotion at room temperature；0.22g emulsifiers II and 10ml deionized waters are stirred
Mixing is mixed, emulsifier aqueous solution is configured to, 12.3g shell monomers are added dropwise, pre-emulsification 45min is stirred at room temperature and obtains shell monomers
Lotion；
(2) be added dropwise under conditions of being passed through nitrogen and stirring 0.2g initiators (by 0.2g initiators be dissolved in 8ml go from
It is added dropwise after in sub- water) and 6ml nuclear layer monomer lotions, system is then warming up to 85 DEG C, is stirred to react, occurs blue in system
Continue to stir 60min after fluorescence, stops reaction to get seed emulsion；
(3) seed emulsion obtained by (2) step is cooled to 40 DEG C, 0.04g initiators, 1.2g sodium carbonate is at the uniform velocity added dropwise
With 9ml nuclear layer monomer lotions, then system be warming up to 80 DEG C, insulation reaction 45min, propylene acid for adjusting pH value is added to 5, stirring
Then 45min adjusts pH value and obtains stratum nucleare polymer emulsion to 8；
(4) and then in stratum nucleare polymer emulsion 0.04g initiators are added, stirs 15min, 0.06g is then added dropwise successively
Emulsifier III, the shell monomers lotion and 0.08g sodium bicarbonates, then system be warming up to 90 DEG C, insulation reaction 1.5 hours；
Propylene acid for adjusting pH value is added in system obtained by (5) (4) steps to 5, is stirred to react 60min, 4ml pines are then added
(rosin is 1 with toluene mass ratio to fragrant toluene solution：1.2) 15min is stirred, system temperature is down to room temperature discharging to get described
Acrylate copolymer mother liquor.
The emulsifier I is the mixture of lauryl sodium sulfate and Nonyl pheno base ether, and weight ratio is
1：5；The emulsifier II is made of disproportionation rosin acid potassium, potassium oleate and Nonyl pheno base ether, weight ratio 2：
1.5：1；The emulsifier III is sodium vinyl sulfonate；The initiator is ammonium persulfate；The nuclear layer monomer be acrylamide,
The mixture of methyl methacrylate and Isooctyl acrylate monomer, weight ratio 1：0.8：1.4；The shell monomers are inclined fluorine
The mixture of ethylene, methylpropene sodium sulfonate, styrene and Isobutyl methacrylate, weight ratio 1：0.3：0.5：
0.5。
Embodiment 3
Embodiment 3 provides a kind of acrylic acid glue for tile, the acrylic acid glue for tile, in parts by weight, including acrylic acid
Ester copolymer mother liquor 42, bleeding agent 0.8, water 57；The bleeding agent is sodium dioctyl sulfosuccinate.
The preparation method of the acrylate copolymer mother liquor includes the following steps：
(1) 0.2g emulsifiers I and 15ml deionized waters are stirred, are configured to emulsifier aqueous solution, 19.0g cores are added dropwise
Layer monomer stirs pre-emulsification 40min and obtains nuclear layer monomer lotion at room temperature；0.22g emulsifiers II and 10ml deionized waters are stirred
Mixing is mixed, emulsifier aqueous solution is configured to, 12.3g shell monomers are added dropwise, pre-emulsification 40min is stirred at room temperature and obtains shell monomers
Lotion；
(2) be added dropwise under conditions of being passed through nitrogen and stirring 0.2g initiators (by 0.2g initiators be dissolved in 8ml go from
It is added dropwise after in sub- water) and 6ml nuclear layer monomer lotions, system is then warming up to 85 DEG C, is stirred to react, occurs blue in system
Continue to stir 60min after fluorescence, stops reaction to get seed emulsion；
(3) seed emulsion obtained by (2) step is cooled to 35 DEG C, 0.04g initiators, 1.2g sodium carbonate is at the uniform velocity added dropwise
With 9ml nuclear layer monomer lotions, then system be warming up to 80 DEG C, insulation reaction 45min, propylene acid for adjusting pH value is added to 4, stirring
Then 45min adjusts pH value and obtains stratum nucleare polymer emulsion to 8；
(4) and then in stratum nucleare polymer emulsion 0.04g initiators are added, stirs 15min, 0.06g is then added dropwise successively
Emulsifier III, the shell monomers lotion and 0.08g sodium bicarbonates, then system be warming up to 90 DEG C, insulation reaction 1.5 hours；
Propylene acid for adjusting pH value is added in system obtained by (5) (4) steps to 5, is stirred to react 60min, 4ml pines are then added
(rosin is 1 with toluene mass ratio to fragrant toluene solution：1.2) 15min is stirred, system temperature is down to room temperature discharging to get described
Acrylate copolymer mother liquor.
The emulsifier I is the mixture of lauryl sodium sulfate and Nonyl pheno base ether, and weight ratio is
1：5；The emulsifier II is made of disproportionation rosin acid potassium, potassium oleate and Nonyl pheno base ether, and weight ratio is
1.8：1.2：1；The emulsifier III is sodium vinyl sulfonate；The initiator is ammonium persulfate；The nuclear layer monomer is propylene
The mixture of amide, methyl methacrylate and Isooctyl acrylate monomer, weight ratio 1：0.7：1.3；The shell monomers
For the mixture of vinylidene, methylpropene sodium sulfonate, styrene and Isobutyl methacrylate, weight ratio 1：0.2：
0.35：0.35.
Embodiment 4
Embodiment 4 provides a kind of acrylic acid glue for tile, the acrylic acid glue for tile, in parts by weight, including acrylic acid
Ester copolymer mother liquor 42, bleeding agent 0.8, water 57；The bleeding agent is sodium dioctyl sulfosuccinate.
The preparation method of the acrylate copolymer mother liquor includes the following steps：
(1) 0.2g emulsifiers I and 15ml deionized waters are stirred, are configured to emulsifier aqueous solution, 19.0g cores are added dropwise
Layer monomer stirs pre-emulsification 40min and obtains nuclear layer monomer lotion at room temperature；0.22g emulsifiers II and 10ml deionized waters are stirred
Mixing is mixed, emulsifier aqueous solution is configured to, 12.3g shell monomers are added dropwise, pre-emulsification 40min is stirred at room temperature and obtains shell monomers
Lotion；
(2) be added dropwise under conditions of being passed through nitrogen and stirring 0.2g initiators (by 0.2g initiators be dissolved in 8ml go from
It is added dropwise after in sub- water) and 6ml nuclear layer monomer lotions, system is then warming up to 85 DEG C, is stirred to react, occurs blue in system
Continue to stir 60min after fluorescence, stops reaction to get seed emulsion；
(3) seed emulsion obtained by (2) step is cooled to 35 DEG C, 0.04g initiators, 1.2g sodium carbonate is at the uniform velocity added dropwise
With 9ml nuclear layer monomer lotions, then system be warming up to 80 DEG C, insulation reaction 45min, propylene acid for adjusting pH value is added to 4, stirring
Then 45min adjusts pH value and obtains stratum nucleare polymer emulsion to 8；
(4) and then in stratum nucleare polymer emulsion 0.04g initiators are added, stirs 15min, 0.06g is then added dropwise successively
Emulsifier III, the shell monomers lotion and 0.08g sodium bicarbonates, then system be warming up to 90 DEG C, insulation reaction 1.5 hours；
Propylene acid for adjusting pH value is added in system obtained by (5) (4) steps to 5, is stirred to react 60min, 4ml pines are then added
(rosin is 1 with toluene mass ratio to fragrant toluene solution：1.2) 15min is stirred, system temperature is down to room temperature discharging to get described
Acrylate copolymer mother liquor.
The emulsifier I is the mixture of lauryl sodium sulfate and Nonyl pheno base ether, and weight ratio is
1：5；The emulsifier II is made of disproportionation rosin acid potassium, potassium oleate and Nonyl pheno base ether, and weight ratio is
1.8：1.2：1；The emulsifier III is sodium vinyl sulfonate；The initiator is ammonium persulfate；The nuclear layer monomer is propylene
The mixture of amide, methyl methacrylate and methyl acrylate, weight ratio 1：0.7：1.3；The shell monomers are
The mixture of vinylidene, methylpropene sodium sulfonate, styrene and Isobutyl methacrylate, weight ratio 1：0.2：
0.35：0.35.
Embodiment 5
Embodiment 5 provides a kind of acrylic acid glue for tile, the acrylic acid glue for tile, in parts by weight, including acrylic acid
Ester copolymer mother liquor 42, bleeding agent 0.8, water 57；The bleeding agent is sodium dioctyl sulfosuccinate.
The preparation method of the acrylate copolymer mother liquor includes the following steps：
(1) 0.2g emulsifiers I and 15ml deionized waters are stirred, are configured to emulsifier aqueous solution, 19.0g cores are added dropwise
Layer monomer stirs pre-emulsification 40min and obtains nuclear layer monomer lotion at room temperature；0.22g emulsifiers II and 10ml deionized waters are stirred
Mixing is mixed, emulsifier aqueous solution is configured to, 12.3g shell monomers are added dropwise, pre-emulsification 40min is stirred at room temperature and obtains shell monomers
Lotion；
(2) be added dropwise under conditions of being passed through nitrogen and stirring 0.2g initiators (by 0.2g initiators be dissolved in 8ml go from
It is added dropwise after in sub- water) and 6ml nuclear layer monomer lotions, system is then warming up to 85 DEG C, is stirred to react, occurs blue in system
Continue to stir 60min after fluorescence, stops reaction to get seed emulsion；
(3) seed emulsion obtained by (2) step is cooled to 35 DEG C, 0.04g initiators, 1.2g sodium carbonate is at the uniform velocity added dropwise
With 9ml nuclear layer monomer lotions, then system be warming up to 80 DEG C, insulation reaction 45min, propylene acid for adjusting pH value is added to 4, stirring
Then 45min adjusts pH value and obtains stratum nucleare polymer emulsion to 8；
(4) and then in stratum nucleare polymer emulsion 0.04g initiators are added, stirs 15min, 0.06g is then added dropwise successively
Emulsifier III, the shell monomers lotion and 0.08g sodium bicarbonates, then system be warming up to 90 DEG C, insulation reaction 1.5 hours；
Propylene acid for adjusting pH value is added in system obtained by (5) (4) steps to 5, is stirred to react 60min, 4ml pines are then added
(rosin is 1 with toluene mass ratio to fragrant toluene solution：1.2) 15min is stirred, system temperature is down to room temperature discharging to get described
Acrylate copolymer mother liquor.
The emulsifier I is the mixture of lauryl sodium sulfate and Nonyl pheno base ether, and weight ratio is
1：5；The emulsifier II is made of disproportionation rosin acid potassium, potassium oleate and Nonyl pheno base ether, and weight ratio is
1.8：1.2：1；The emulsifier III is sodium vinyl sulfonate；The initiator is ammonium persulfate；The nuclear layer monomer is propylene
The mixture of amide, Isobutyl methacrylate and Isooctyl acrylate monomer, weight ratio 1：0.7：1.3；The shell list
Body is the mixture of vinylidene, methylpropene sodium sulfonate, styrene and Isobutyl methacrylate, weight ratio 1：
0.2：0.35：0.35.
Embodiment 6
Embodiment 6 provides a kind of acrylic acid glue for tile, the acrylic acid glue for tile, in parts by weight, including acrylic acid
Ester copolymer mother liquor 42, bleeding agent 0.8, water 57；The bleeding agent is sodium dioctyl sulfosuccinate.
The preparation method of the acrylate copolymer mother liquor includes the following steps：
(1) 0.2g emulsifiers I and 15ml deionized waters are stirred, are configured to emulsifier aqueous solution, 19.0g cores are added dropwise
Layer monomer stirs pre-emulsification 40min and obtains nuclear layer monomer lotion at room temperature；0.22g emulsifiers II and 10ml deionized waters are stirred
Mixing is mixed, emulsifier aqueous solution is configured to, 12.3g shell monomers are added dropwise, pre-emulsification 40min is stirred at room temperature and obtains shell monomers
Lotion；
(2) 0.2g initiators are added dropwise under conditions of being passed through nitrogen and stirring and (0.2g initiators are dissolved in 8ml deionizations
It is added dropwise after in water) and 6ml nuclear layer monomer lotions, system is then warming up to 85 DEG C, is stirred to react, it is glimmering to occur blue in system
Continue to stir 60min after light, stops reaction to get seed emulsion；
(3) seed emulsion obtained by (2) step is cooled to 35 DEG C, 0.04g initiators, 1.2g sodium carbonate is at the uniform velocity added dropwise
With 9ml nuclear layer monomer lotions, then system be warming up to 80 DEG C, insulation reaction 45min, propylene acid for adjusting pH value is added to 4, stirring
Then 45min adjusts pH value and obtains stratum nucleare polymer emulsion to 8；
(4) and then in stratum nucleare polymer emulsion 0.04g initiators are added, stirs 15min, 0.06g is then added dropwise successively
Emulsifier III, the shell monomers lotion and 0.08g sodium bicarbonates, then system be warming up to 90 DEG C, insulation reaction 1.5 hours；
Propylene acid for adjusting pH value is added in system obtained by (5) (4) steps to 5, is stirred to react 60min, 4ml pines are then added
(rosin is 1 with toluene mass ratio to fragrant toluene solution：1.2) 15min is stirred, system temperature is down to room temperature discharging to get described
Acrylate copolymer mother liquor.
The emulsifier I is the mixture of lauryl sodium sulfate and Nonyl pheno base ether, and weight ratio is
1：5；The emulsifier II is made of disproportionation rosin acid potassium, potassium oleate and Nonyl pheno base ether, and weight ratio is
1.8：1.2：1；The emulsifier III is Nonyl pheno base ether；The initiator is ammonium persulfate；The nuclear layer monomer
For the mixture of acrylamide, methyl methacrylate and Isooctyl acrylate monomer, weight ratio 1：0.7：1.3；The shell
Layer monomer is the mixture of vinylidene, methylpropene sodium sulfonate, styrene and Isobutyl methacrylate, and weight ratio is
1：0.2：0.35：0.35.
Comparative example 1
Comparative example 1 provides a kind of acrylic acid glue for tile, the acrylic acid glue for tile, in parts by weight, including acrylic acid
Ester copolymer mother liquor 42, bleeding agent 0.8, water 57；The bleeding agent is sodium dioctyl sulfosuccinate.
The preparation method difference from Example 3 of the acrylate copolymer mother liquor is the emulsifier II by oil
Sour potassium and Nonyl pheno base ether composition, weight ratio 1.2：1.
Comparative example 2
Comparative example 2 provides a kind of acrylic acid glue for tile, the acrylic acid glue for tile, in parts by weight, including acrylic acid
Ester copolymer mother liquor 42, bleeding agent 0.8, water 57；The bleeding agent is sodium dioctyl sulfosuccinate.
The preparation method difference from Example 3 of the acrylate copolymer mother liquor is the emulsifier II by qi
Change potassium rosinate and Nonyl pheno base ether composition, weight ratio 1.8：1.
Comparative example 3
Comparative example 3 provides a kind of acrylic acid glue for tile, the acrylic acid glue for tile, in parts by weight, including acrylic acid
Ester copolymer mother liquor 42, bleeding agent 0.8, water 57；The bleeding agent is sodium dioctyl sulfosuccinate.
The preparation method difference from Example 3 of the acrylate copolymer mother liquor is that the nuclear layer monomer is first
The mixture of base methyl acrylate and Isooctyl acrylate monomer, weight ratio 0.7：1.3.
Comparative example 4
Comparative example 4 provides a kind of acrylic acid glue for tile, the acrylic acid glue for tile, in parts by weight, including acrylic acid
Ester copolymer mother liquor 42, bleeding agent 0.8, water 57；The bleeding agent is sodium dioctyl sulfosuccinate.
The preparation method difference from Example 3 of the acrylate copolymer mother liquor is that the shell monomers are first
The mixture of base sodium allylsulfonate, styrene and Isobutyl methacrylate, weight ratio 0.2： 0.35：0.35.
Comparative example 5
Comparative example 5 provides a kind of acrylic acid glue for tile, the acrylic acid glue for tile, in parts by weight, including acrylic acid
Ester copolymer mother liquor 42, bleeding agent 0.8, water 57；The bleeding agent is sodium dioctyl sulfosuccinate.
The preparation method difference from Example 3 of the acrylate copolymer mother liquor is inclined fluorine in the shell monomers
The mixture of ethylene, styrene and Isobutyl methacrylate, weight ratio 1：0.35：0.35.
Comparative example 6
Comparative example 6 provides a kind of acrylic acid glue for tile, the acrylic acid glue for tile, in parts by weight, including acrylic acid
Ester copolymer mother liquor 42, bleeding agent 0.8, water 57；The bleeding agent is sodium dioctyl sulfosuccinate.
The preparation method difference from Example 3 of the acrylate copolymer mother liquor is that the shell monomers are inclined
The mixture of vinyl fluoride, methylpropene sodium sulfonate and styrene, weight ratio 1：0.2：0.35.
Comparative example 7
Comparative example 7 provides a kind of acrylic acid glue for tile, the acrylic acid glue for tile, in parts by weight, including acrylic acid
Ester copolymer mother liquor 42, bleeding agent 0.8, water 57；The bleeding agent is sodium dioctyl sulfosuccinate.
The preparation method of the acrylate copolymer mother liquor includes the following steps：
(1) 0.2g emulsifiers I and 15ml deionized waters are stirred, are configured to emulsifier aqueous solution, 19.0g cores are added dropwise
Layer monomer stirs pre-emulsification 40min and obtains nuclear layer monomer lotion at room temperature；0.22g emulsifiers II and 10ml deionized waters are stirred
Mixing is mixed, emulsifier aqueous solution is configured to, 12.3g shell monomers are added dropwise, pre-emulsification 40min is stirred at room temperature and obtains shell monomers
Lotion；
(2) be added dropwise under conditions of being passed through nitrogen and stirring 0.2g initiators (by 0.2g initiators be dissolved in 8ml go from
It is added dropwise after in sub- water) and 6ml nuclear layer monomer lotions, system is then warming up to 85 DEG C, is stirred to react, occurs blue in system
Continue to stir 60min after fluorescence, stops reaction to get seed emulsion；
(3) seed emulsion obtained by (2) step is cooled to 35 DEG C, 0.04g initiators and 9ml stratum nucleare lists is at the uniform velocity added dropwise
Precursor emulsion, then system be warming up to 80 DEG C, insulation reaction 45min, propylene acid for adjusting pH value is added to 4, stirs 45min, then
It adjusts pH value and obtains stratum nucleare polymer emulsion to 8；
(4) and then in stratum nucleare polymer emulsion 0.04g initiators are added, stirs 15min, 0.06g is then added dropwise successively
Emulsifier III, the shell monomers lotion and 0.08g sodium bicarbonates, then system be warming up to 90 DEG C, insulation reaction 1.5 hours；
Propylene acid for adjusting pH value is added in system obtained by (5) (4) steps to 5, is stirred to react 60min, 4ml pines are then added
(rosin is 1 with toluene mass ratio to fragrant toluene solution：1.2) 15min is stirred, system temperature is down to room temperature discharging to get described
Acrylate copolymer mother liquor.
The emulsifier I is the mixture of lauryl sodium sulfate and Nonyl pheno base ether, and weight ratio is
1：5；The emulsifier II is made of disproportionation rosin acid potassium, potassium oleate and Nonyl pheno base ether, and weight ratio is
1.8：1.2：1；The emulsifier III is sodium vinyl sulfonate；The initiator is ammonium persulfate；The nuclear layer monomer is propylene
The mixture of amide, methyl methacrylate and Isooctyl acrylate monomer, weight ratio 1：0.7：1.3；The shell monomers
For the mixture of vinylidene, methylpropene sodium sulfonate, styrene and Isobutyl methacrylate, weight ratio 1：0.2：
0.35：0.35.
Comparative example 8
Comparative example 8 provides a kind of acrylic acid glue for tile, the acrylic acid glue for tile, in parts by weight, including acrylic acid
Ester copolymer mother liquor 42, bleeding agent 0.8, water 57；The bleeding agent is sodium dioctyl sulfosuccinate.
The preparation method of the acrylate copolymer mother liquor includes the following steps：
(1) 0.2g emulsifiers I and 15ml deionized waters are stirred, are configured to emulsifier aqueous solution, 19.0g cores are added dropwise
Layer monomer stirs pre-emulsification 40min and obtains nuclear layer monomer lotion at room temperature；0.22g emulsifiers II and 10ml deionized waters are stirred
Mixing is mixed, emulsifier aqueous solution is configured to, 12.3g shell monomers are added dropwise, pre-emulsification 40min is stirred at room temperature and obtains shell monomers
Lotion；
(2) be added dropwise under conditions of being passed through nitrogen and stirring 0.2g initiators (by 0.2g initiators be dissolved in 8ml go from
It is added dropwise after in sub- water) and 6ml nuclear layer monomer lotions, system is then warming up to 85 DEG C, is stirred to react, occurs blue in system
Continue to stir 60min after fluorescence, stops reaction to get seed emulsion；
(3) seed emulsion obtained by (2) step is cooled to 35 DEG C, 0.04g initiators, 1.2g sodium carbonate is at the uniform velocity added dropwise
With 9ml nuclear layer monomer lotions, then system be warming up to 80 DEG C, insulation reaction 45min, propylene acid for adjusting pH value is added to 4, stirring
Then 45min adjusts pH value and obtains stratum nucleare polymer emulsion to 8；
(4) and then in stratum nucleare polymer emulsion the shell monomers lotion, 0.06g emulsifiers III, 0.04g are added dropwise successively
Initiator and 0.08g sodium bicarbonates, then system be warming up to 90 DEG C, insulation reaction 1.5 hours；
Propylene acid for adjusting pH value is added in system obtained by (5) (4) steps to 5, is stirred to react 60min, 4ml pines are then added
(rosin is 1 with toluene mass ratio to fragrant toluene solution：1.2) 15min is stirred, system temperature is down to room temperature discharging to get described
Acrylate copolymer mother liquor.
The emulsifier I is the mixture of lauryl sodium sulfate and Nonyl pheno base ether, and weight ratio is
1：5；The emulsifier II is made of disproportionation rosin acid potassium, potassium oleate and Nonyl pheno base ether, and weight ratio is
1.8：1.2：1；The emulsifier III is sodium vinyl sulfonate；The initiator is ammonium persulfate；The nuclear layer monomer is propylene
The mixture of amide, methyl methacrylate and Isooctyl acrylate monomer, weight ratio 1：0.7：1.3；The shell monomers
For the mixture of vinylidene, methylpropene sodium sulfonate, styrene and Isobutyl methacrylate, weight ratio 1：0.2：
0.35：0.35.
Comparative example 9
Comparative example 9 provides a kind of acrylic acid glue for tile, the acrylic acid glue for tile, in parts by weight, including acrylic acid
Ester copolymer mother liquor 42, bleeding agent 0.8, water 57；The bleeding agent is sodium dioctyl sulfosuccinate.
The preparation method of the acrylate copolymer mother liquor includes the following steps：
(1) 0.2g emulsifiers II and 15ml deionized waters are stirred, are configured to emulsifier aqueous solution, 19.0g is added dropwise
Nuclear layer monomer stirs pre-emulsification 40min and obtains nuclear layer monomer lotion at room temperature；0.22g emulsifiers I and 10ml deionized waters are stirred
Mixing is mixed, emulsifier aqueous solution is configured to, 12.3g shell monomers are added dropwise, pre-emulsification 40min is stirred at room temperature and obtains shell monomers
Lotion；
(2) be added dropwise under conditions of being passed through nitrogen and stirring 0.2g initiators (by 0.2g initiators be dissolved in 8ml go from
It is added dropwise after in sub- water) and 6ml nuclear layer monomer lotions, system is then warming up to 85 DEG C, is stirred to react, occurs blue in system
Continue to stir 60min after fluorescence, stops reaction to get seed emulsion；
(3) seed emulsion obtained by (2) step is cooled to 35 DEG C, 0.04g initiators, 1.2g sodium carbonate is at the uniform velocity added dropwise
With 9ml nuclear layer monomer lotions, then system be warming up to 80 DEG C, insulation reaction 45min, propylene acid for adjusting pH value is added to 4, stirring
Then 45min adjusts pH value and obtains stratum nucleare polymer emulsion to 8；
(4) and then in stratum nucleare polymer emulsion 0.04g initiators are added, stirs 15min, 0.06g is then added dropwise successively
Emulsifier III, the shell monomers lotion and 0.08g sodium bicarbonates, then system be warming up to 90 DEG C, insulation reaction 1.5 hours；
Propylene acid for adjusting pH value is added in system obtained by (5) (4) steps to 5, is stirred to react 60min, 4ml pines are then added
(rosin is 1 with toluene mass ratio to fragrant toluene solution：1.2) 15min is stirred, system temperature is down to room temperature discharging to get described
Acrylate copolymer mother liquor.
The emulsifier I is the mixture of lauryl sodium sulfate and Nonyl pheno base ether, and weight ratio is
1：5；The emulsifier II is made of disproportionation rosin acid potassium, potassium oleate and Nonyl pheno base ether, and weight ratio is
1.8：1.2：1；The emulsifier III is sodium vinyl sulfonate；The initiator is ammonium persulfate；The nuclear layer monomer is propylene
The mixture of amide, methyl methacrylate and Isooctyl acrylate monomer, weight ratio 1：0.7：1.3；The shell monomers
For the mixture of vinylidene, methylpropene sodium sulfonate, styrene and Isobutyl methacrylate, weight ratio 1：0.2：
0.35：0.35.
Performance evaluation
1. height temperature stability
Freeze-thaw stability：Appropriate lotion is placed into 16h at -50 DEG C, 8h is then placed at 25 DEG C, is recycled 5 times, observation
Whether appearance demulsification, creaming of emulsion.50 DEG C of storage stabilities of lotion：Appropriate lotion is placed in the wide-mouth bottle of 100mL,
20h is placed in 50 DEG C of insulating box, cools down 3h at room temperature, and no demulsification or lamination occur.According to occurring after freeze thawing treatment
Demulsification, layering, it is rotten situations such as seriousness result is divided into 1~10 grade, wherein 1 is the shakinesses such as do not occur being demulsified
Pledge love condition, 10 is worst for stability, situations such as serious demulsification, milk particle is reunited occurs.Likewise, by the lotion after high-temperature process
Analysis of stability is 1~5 grade, and 1 is best for stability, and 5 is worst.
2. mechanical performance
The glue for tile provided the embodiment of the present application and comparative example uses cross-cut methods, standard JC/T 547-2005《Ceramic wall
Floor tile adhesive》With standard GB/T/T9755-2001《Exterior wall coating material of synthetic resin emulsion》Carry out adhesion strength, gel speed
The performance tests such as rate, peel strength.Wherein mechanical stability is to stir 15min under 2000rp/min rates, is seen whether out
Situations such as being now significantly layered, becoming cloudy, according to muddy degree, rate of deposition it is mostly and few, result is divided into 1~5 grade,
In 1 mechanical stability it is best, 5 is worst.
1 performance test table of table
As can be seen from Table 1, acrylic acid glue for tile provided by the present application has good freeze-thaw stability, high temperature, machinery
The performances such as stability, while there is good adhesive force, tensile bond strength, and still kept after 5 Frozen-thawed cycleds
Very high intensity.In addition, glue for tile provided by the present application has good water resistance.
Example above-mentioned is merely illustrative, some features of the feature for explaining the disclosure.The attached claims
It is intended to the range as wide as possible for requiring to be contemplated that, and embodiments as presented herein is only according to all possible embodiment
Combination selection embodiment explanation.Therefore, the purpose of applicant is that the attached claims are not illustrated the present invention
Feature exemplary selectional restriction.And the progress in science and technology will be formed language express inaccuracy due to and not
The possible equivalent or son being presently considered are replaced, and these variations also should in the conceived case be interpreted by appended
Claim covers.
Claims (10)
1. a kind of acrylic acid glue for tile, which is characterized in that the acrylic acid glue for tile, in parts by weight, including acrylate is total
Polymers mother liquor 40~50, bleeding agent 0.1~1.5, water 50~65；The bleeding agent is sulfonation esters bleeding agent.
2. acrylic acid glue for tile as described in claim 1, which is characterized in that the preparation side of the acrylate copolymer mother liquor
Method includes the following steps：
(1) emulsifier I is stirred with deionized water, is configured to emulsifier aqueous solution, nuclear layer monomer is added dropwise, stirs at room temperature
30~45min of pre-emulsification obtains nuclear layer monomer lotion；Emulsifier II is stirred with deionized water, it is water-soluble to be configured to emulsifier
Shell monomers are added dropwise in liquid, stir 30~45min of pre-emulsification at room temperature and obtain shell monomers lotion；
(2) initiator and nuclear layer monomer lotion is added dropwise under conditions of being passed through nitrogen and stirring, system is then warming up to 75~
It 85 DEG C, is stirred to react, continues 45~60min of stirring after occurring blue-fluorescence in system, stop reaction to get seed emulsion；
(3) seed emulsion obtained by (2) step is cooled to 30~40 DEG C, initiator, sodium carbonate and remaining core is at the uniform velocity added dropwise
Layer monomer emulsions, then system be warming up to 80 DEG C, 30~45min of insulation reaction, propylene acid for adjusting pH value is added to 4~5, stirring
Then 30~45min adjusts pH value and obtains stratum nucleare polymer emulsion to 7~8；
(4) and then in stratum nucleare polymer emulsion initiator is added, stirs 10~15min, emulsifier III, institute are then added dropwise successively
Shell monomers lotion and sodium bicarbonate are stated, then system is warming up to 90 DEG C, insulation reaction 1~1.5 hour；
Propylene acid for adjusting pH value is added in system obtained by (5) (4) steps to 4~5, is stirred to react 45~60min, pine is then added
Fragrant toluene solution stirs 15min, and system temperature is down to room temperature discharging to get the acrylate copolymer mother liquor.
3. acrylic acid glue for tile as claimed in claim 2, which is characterized in that the nuclear layer monomer includes acrylamide and propylene
Esters of gallic acid monomer；The acrylic ester monomer is selected from (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propylene
Sour N-butyl, (methyl) isobutyl acrylate, Isooctyl acrylate monomer, (methyl) acrylic acid, (methyl) glycidyl acrylate,
(methyl) hydroxy-ethyl acrylate, it is one or more in (methyl) hydroxypropyl acrylate.
4. acrylic acid glue for tile as claimed in claim 2, which is characterized in that the shell monomers include vinylidene, methyl
Sodium allylsulfonate, styrene and Isobutyl methacrylate, weight ratio 1：(0.1~0.3)：(0.2~0.5)：(0.2
~0.5).
5. acrylic acid glue for tile as claimed in claim 4, which is characterized in that the shell monomers include vinylidene, methyl
Sodium allylsulfonate, styrene and Isobutyl methacrylate, weight ratio 1：0.2：0.35：0.35.
6. acrylic acid glue for tile as claimed in claim 2, which is characterized in that the emulsifier I is anion emulsifier and non-
The mixture of ion emulsification；The weight ratio of the anion emulsifier and nonionic emulsifier is 1：(3~5).
7. acrylic acid glue for tile as claimed in claim 2, which is characterized in that the emulsifier II is by disproportionation rosin acid potassium, oil
Sour potassium and Nonyl pheno base ether composition, weight ratio are (1.5~2)：(0.8~1.5)：1.
8. acrylic acid glue for tile as described in claim 1, which is characterized in that gained raw material after the acrylic acid glue for tile drying
Glass transition temperature be -45~-35 DEG C.
9. acrylic acid glue for tile as described in claim 1, which is characterized in that gained raw material after the acrylic acid glue for tile drying
Decomposition temperature be 430~450 DEG C.
10. the application of acrylic acid glue for tile as claimed in any one of claims 1 to 9 wherein, which is characterized in that be applied to ceramic tile
It pastes.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810371172.8A CN108517190A (en) | 2018-04-24 | 2018-04-24 | A kind of acrylic acid glue for tile and its application |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810371172.8A CN108517190A (en) | 2018-04-24 | 2018-04-24 | A kind of acrylic acid glue for tile and its application |
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Cited By (3)
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| CN109943181A (en) * | 2019-03-25 | 2019-06-28 | 付中 | A kind of on-slip coating and preparation method thereof |
| CN114409342A (en) * | 2022-02-14 | 2022-04-29 | 清远楼邦建材科技有限公司 | Preparation method of ceramic tile glue |
| WO2024146075A1 (en) * | 2023-01-04 | 2024-07-11 | 宁德时代新能源科技股份有限公司 | Adhesive and preparation method therefor, and separator, electrode assembly, battery cell, battery, and electric device |
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Application publication date: 20180911 |