CN107033810B - Adhesive alpha-olefin inter - Google Patents
Adhesive alpha-olefin inter Download PDFInfo
- Publication number
- CN107033810B CN107033810B CN201710414322.4A CN201710414322A CN107033810B CN 107033810 B CN107033810 B CN 107033810B CN 201710414322 A CN201710414322 A CN 201710414322A CN 107033810 B CN107033810 B CN 107033810B
- Authority
- CN
- China
- Prior art keywords
- polypropylene
- mass parts
- adhesive
- content
- polyolefin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/10—Homopolymers or copolymers of propene
- C09J123/12—Polypropene
-
- 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
-
- 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
- C09J11/08—Macromolecular additives
-
- 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
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
- C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C09J123/0853—Vinylacetate
-
- 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
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/10—Homopolymers or copolymers of propene
- C09J123/14—Copolymers of propene
-
- 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
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention is a kind of adhesive alpha-olefin inter, comprising: Polypropylene-based graft object, non-grafted polypropylene, the polyolefin or polyolefin derivative object different from above-mentioned the two；With the total amount of above-mentioned three kinds of components be 100 mass parts when, make the content a mass parts of the Polypropylene-based graft object, the content that the non-grafted polyacrylic content is b mass parts, the polyolefin or polyolefin derivative object is c mass parts, meet following relationship: 2 < a < 40, -30 < a-0.435b+0.202c < 10；The Polypropylene-based graft object is obtained from being grafted on acidic materials on polypropylene and/or polypropylene elastomer.Effect of the invention is that obtaining higher bonding force under the premise of avoiding or reducing using other thickening means, to maintain simple process and lower cost, and make the excellent combination property of adhesive.
Description
Technical field
The present invention is a kind of adhesive, specifically a kind of adhesive based on polyacrylate compound.
Background technique
Polypropylene is widely used in holding since nontoxic, tasteless, density is smaller, rigidity, intensity, cheap etc. advantage
The fields such as device, packaging, adhesive.
As adhesive, it is usually required mainly for have the characteristics that following two, (1) bonding force is strong, and the object being stuck will not be random
It falls off；(2) adhesive itself has enough rigidity and intensity, will not be broken the object for causing to be stuck because of adhesive layer ontology
Division.Further for special application field, such as construction material, it is difficult to dismantle again substantially to return after building up due to building
It repairs, it is necessary to assure the adhesive used in it for bonding various building materials has higher stability, needs with the time
Long-term passage still keeps to decompose/degrading or lose bonding force.Again such as when for packaging material food, lithium battery,
It needs to meet without toxic additive the relevant criterion of health and environmental protection, and also wants to decompose/degrade or lose after the heating
Bonding force.Further, since the adhesive in many fields is all wanted larger numbers of and used, thus obtaining suitable bonding force
Under the premise of, it as far as possible using easily available starting materials and easy technical process, reduces and uses additional additive etc., thus convenient
It is mass produced and reduces cost.
And for common polypropylene binders, although maintaining the plurality of advantages of polypropylene itself, its bonding force exists
It is in the application in many fields and insufficient.For this purpose, polypropylene binders known in the prior art have used respectively according to its needs
Additive/modifying agent etc. of kind of various kinds, but common additive is since there is no above-mentioned advantages as polypropylene for itself, in reality
Often become short slab in the application of border, such as that there are stability is insufficient, has the problems such as certain toxicity, therefore, in order to avoid this kind of
Problem directly is implemented to be modified in practice to polypropylene, for example, it is a kind of very convenient that organic acid, which is directly grafted on polypropylene,
Method.
In general, polyacrylate compound by with being blended of these additives, be grafted and etc. after bonding force have
It is promoted, but is accompanied by polyacrylic degradation simultaneously in grafting process, so that the molecular weight of graft product sharply declines.
In follow-up gluing agent preparation, the graft intermediate of excessive degradation can be such that the oligomer in final product adhesive increases,
To influence the hot property, mechanical property and machine-shaping property of adhesive.
For example, document US20060084764, US4698395, US5041338, US5137975, US7713636 are disclosed
Similar method uses the polypropylene of acid grafting as adhesive ingredients.
US5041338 does not further investigate other components too much except using graft polypropylene, component
Also relatively simple, comprehensive performance and bonding force are with all relatively more general from the point of view of standard in recent years.On the basis of this kind of graft polypropylene,
Also there are various improved methods to graft polypropylene in other above-mentioned open source literatures, still, in US20060084764,
It has very high structural requirement to polypropylene itself, and inconvenience is directly chosen commercially available polypropylene and used；It is special in US4698395
It devises and the unnecessary substance being grafted in polyacrylic grafting process is cleaned, reused after being purified；US5137975
It is equally how restricted to manufacturing process；US7713636 has many restrictions to raw material parameter.These can all cause to be mass produced
When technique is inconvenient or cost increase.In addition, the product in above-mentioned document is as the bonding force of adhesive and other a variety of property
Can on remained on room for improvement.
Summary of the invention
It is an object of the present invention to provide one kind in order to avoid the above problem and contain adhesive alpha-olefin inter, by suitable
Formula adjust, using the materials such as handy polypropylene, and avoid or reduce use additive under the premise of obtain compared with
High bonding force.It should be noted that the present invention is not that other means cannot be used to viscosify, but formula of the invention is not
Very high bonding force can be obtained under the premise of being viscosified with other means, if on this basis there are also further requirement, according to
Other thickening means so can be used.
Another object of the present invention is to due to that need not add excessive various additives or using other auxiliary
Property thickening means etc. can also obtain biggish bonding force, also would not influence the excellent of polypropylene itself because of these thickening means
Heterogeneity, such as its hot property, workability, mechanical property can be kept under the premise of obtaining larger bonding force.Therefore, it is mentioning
On the basis of rising bonding force, excellent balance of the adhesive in various performances can be kept.
Another object of the present invention is to, using the raw material and simple preparation process being easily obtained, for example, it is common
Squeezing out blending technology can be completed manufacture, and simple process is suitable for large-scale production.
The present invention is a kind of adhesive alpha-olefin inter, comprising:
Polypropylene-based graft object,
Non-grafted polypropylene,
The polyolefin or polyolefin derivative object different from above-mentioned the two；
With the total amount of above-mentioned three kinds of components be 100 mass parts when, wherein the content of the Polypropylene-based graft object be a matter
Amount part, the content that the non-grafted polyacrylic content is b mass parts, the polyolefin or polyolefin derivative object are c mass parts,
Meet following relationship:
2 < a < 40,
-30<a-0.435b+0.202c<10；
The Polypropylene-based graft object is to be grafted on acidic materials on polypropylene and/or polypropylene elastomer and obtain
's.
Effect of the invention is that obtaining higher bonding under the premise of avoiding or reducing using other thickening means
Power to maintain simple process and lower cost, and makes the excellent combination property of adhesive.
Specific embodiment
Hereinafter, present invention be described in more detail in conjunction with the embodiments, but the following contents and it is not construed as limiting the present invention limitation,
Under the premise of not departing from invention objective of the invention, modification or change appropriate, the scheme after this kind of modification or change can be carried out
It still falls in protection scope of the present invention.
" % ", " part " used in the present invention etc. describes the vocabulary or symbol of deal, in the feelings not illustrated separately
Under condition, all refer to quality, i.e. " mass parts ", " quality % " etc..
Term " blending " in the present invention refers to the mode that high temperature extrusion mixing is carried out with extruder unless otherwise instructed.
But other hybrid modes also can be used, as long as mixing can be made uniform on a molecular scale, thorough.
In the present invention, polypropylene and polypropylene elastomer are considered as two different classification, i.e., not by polypropylene elasticity
Stereoscopic is polyacrylic subordinate concept.In the present invention, use elongation at break as benchmark is judged, specifically fracture is stretched
Long rate is defined as polypropylene elastomer in 1000% or more polypropylene material.
The present invention for ease of description, hereinafter uses following english abbreviations when needed, such as illustrates without other, after
The english abbreviation that text uses and compareing for its meaning are as follows.
G-PP graft polypropylene
G-PPE graft polypropylene elastomer
G-PP/PPE polypropylene/polypropylene elastomer cograft object
HPP homopolypropylene
PPR copolymer polypropylene
BPP branched p 0 lypropylene
EVA ethylene-vinyl acetate copolymer
SEBS hydrogenated styrene-butadiene-styrene block copolymers
PPE polypropylene elastomer
PE polyethylene (contains HDPE, MDPE, LDPE, LLDPE, POE)
OBC olefin block copolymers
SIS styrene-isoprene-styrene block copolymer
HIPS high impact polystyrene
GPPS general purpose polystyrene
HDPE high density polyethylene (HDPE)
MDPE medium density polyethylene
LDPE low density polyethylene (LDPE)
LLDPE linear low density polyethylene
POE polyethylene elastomer
[adhesive]
Adhesive alpha-olefin inter of the invention, including following three classes component:
(i) Polypropylene-based graft object, mainly bonding force can be improved in graft polypropylene, but can lose some polypropylene sheets
The performance of body.
(ii) non-grafted polypropylene, non-grafted polypropylene can be better maintained the performance of polypropylene itself, with grafting
Agent polypropylene carries out complementation in effect.
(iii) from both above-mentioned different polyolefin or polyolefin derivative object, make polyolefin or polyolefin derivative object and upper
It states (i), when (ii) coexists, reconciliation can be played the role of, so that both above-mentioned respective advantage maintains to a greater extent；
In the present invention, " polyolefin or polyolefin derivative object different from above-mentioned the two " refer to, in same a adhesive,
If a certain PP type compound has been used as (i), the component in (ii) to use, component (iii) is used as no longer to add
The compound.For example, if above-mentioned (i) uses branched p 0 lypropylene using the homopolypropylene of grafting, (ii), as (iii)
Component no longer adds both compounds.For another example if not using branched p 0 lypropylene in (ii), but used
Poly- polypropylene is then used as component (iii), can still add branched p 0 lypropylene again.Further, it is preferable to not use propylene wherein
Class compound.
Details about the component (i), it is preferred to use remembered in Chinese patent application the 201710061443.5th
Carry using polypropylene and/or polypropylene elastomer as graft is formed by when being graft polymerized object, herein with the side of reference
Formula charges to entire contents.Component (ii), (iii) are not particularly limited, and commercially available product (such as table 3, table 4 can be used when preparing
Cited, the ontology hybrid mode of graft is preferably such as table 5).
Inventor also found, after the three kinds of above components meet specific content, grafting can be kept to connect with non-simultaneously
The polyacrylic advantage of branch obtains the preferable adhesive of balance between bonding force height, multiple performance.Based on such purpose, originally
Component needed for invention is as follows:
With the total amount of above-mentioned three kinds of components be 100 mass parts when, wherein the content of the Polypropylene-based graft object be a matter
Amount part, the content that the non-grafted polyacrylic content is b mass parts, the polyolefin or polyolefin derivative object are c mass parts,
Meet following relationship:
2 < a < 40, ingredient needed for Polypropylene-based graft object is to maintain adhesive, according to the needs to bonding force can 2~
It is adjusted between 40 parts, for the angle for improving adhesive, preferably 5 parts or more of lower limit, more preferable 10 parts or more, more preferable 15
Part or more, further preferred 20 parts or more；Never the angle of performance of polypropylene itself is interfered to set out, preferably 35 parts of the upper limit with
Under, more preferable 30 parts hereinafter, more preferable 25 parts or less.
Under the premise of the content of Polypropylene-based graft object is certain, the relation with contents of preferably three of the above component meets following formula
(I):
The formula of -30 < a-0.435b+0.202c < 10 (I)；
The value i.e. between -30~10, the value range lower limit more preferably -20 or more, more preferably -10 or more, more preferably -
7 or more, the upper limit more preferable 5 hereinafter, more preferable 0 hereinafter, more preferably -3 or less.In such range, it can obtain bigger
Bonding force.
In addition, said components (ii) of the invention, the ratio of (iii) and said components (i), i.e. b/a and c/a, are being improved
Under the purpose of bonding force, range is preferably as follows respectively: b/a=2~10, more preferable 2~5, more preferable 2.2~2.5, c/a=
0.5~3, more preferable 0.8~1.5, c/b=0.1~0.6, more preferable 0.36~0.6, more preferably meet the ratio of this section simultaneously
The value range of range and upper formula (I).
The Polypropylene-based graft object is acid used in the present invention obtained from acid or acid anhydrides are grafted on polypropylene
Or it is preferable to use acrylic acid, maleic acid, maleic anhydride, methacrylic acid, acrylate, methacrylate, clothing health for acid anhydrides
Any one kind or two or more mixture in acid, itaconic anhydride.Acid or acid anhydrides is selected to be not particularly limited, mainly still
It sees that the requirements such as the situation that is evenly distributed, moisture content of final grafting dosage, grafting rate, acidity etc. are selected, can also select
Select the esters of slant acidity.
If being easy to produce phase with Polypropylene-based graft object inventors have found that non-grafted polypropylene elastomer dosage is more
It mutually influences, the comprehensive performance of final products is caused to deteriorate.Therefore, it is suggested that reducing within its dosage, such as 30%, more preferable 20%
Within, more preferable 10% or less.Further preferably it is mixed as the ingredient in (iii) together with other polyolefin (derivative) makes
With can alleviate above-mentioned comprehensive performance and deteriorate.In another preferred embodiment, the present invention does not use non-grafted poly- third
Alkene elastomer.
Further, it is preferable to which polypropylene elastomer is first carried out in Polypropylene-based graft object to grafting is re-used as adhesive
Ingredient, so that final products can retain preferable comprehensive performance and higher grafting rate.Except polypropylene elastomer, this hair
Bright Polypropylene-based graft object can also use one of homopolypropylene, copolymer polypropylene, branched p 0 lypropylene etc. or a variety of,
They can also be shared with polypropylene elastomer.
Following substance, ethylene-vinyl acetate copolymer, hydrogenated styrene-can be used in polyolefin derivative object of the invention
Butadiene-styrene block copolymer, styrene-butadiene be embedding-styrene section copolymer, polypropylene elastomer, polyethylene, alkene
Hydrocarbon block copolymer, styrene-isoprene-styrene block copolymer, high impact polystyrene, general purpose polystyrene, it
Can be used alone wherein any a kind, the mixture of more than two kinds in them also can be used.
Adhesive of the invention preferably all has excellent bonding force to construction material, packaging material etc., for example, to aluminium foil
Bonding force preferred 1.0N/mm or more, more preferable 1.2N/mm or more, more preferable 1.6N/mm or more, more preferable 2N/mm or more,
1.0N/mm or more preferred to the bonding force of PA membrane, more preferable 1.2N/mm or more, more preferable 1.6N/mm or more, more preferably
2N/mm or more, more preferable 2.5N/mm or more, 4.0N/mm or more preferred to the bonding force of aluminium flake, more preferable 5.0N/mm or more,
More preferable 6.0N/mm or more, more preferable 6.5N/mm or more, more preferable 7N/mm or more.The test method of above-mentioned bonding force will be in
It is shown in detail below.
As described above, graft of the invention is formed by the way that acid to be grafted on polymer raw material, the polymer
Containing a kind or more of polypropylene in raw material, the melt index of the graft is the 1.5~30 of the melt index of the raw material
Times, as its lower limit, preferably 2 times, more preferable 3 times, most preferably 5 times, as its upper limit, preferably 20 times, more preferable 10 times, especially
It is preferred that 8 times, most preferably 6 times.
If there was only a kind of polymer in above-mentioned polymer raw material, above-mentioned melt index refers to the molten of the polymer raw material
Melt index, if above-mentioned polymer raw material is the mixture of multiple polymers, above-mentioned melt index is using these polymer
The number mean value of melt index is the melt index of polymer raw material.
In above-mentioned range, adhesive can be easily set to obtain biggish bonding force, and performance is more stable, simultaneously
The degradation of polypropylene base is controllable.When the multiple is excessively high, polyacrylic degradation excessively, is unfavorable for the application as adhesive, and one
Aspect bonding force is streaky uncontrollable, on the other hand, seriously affects the hot property, mechanical property and processing forming of adhesive
Energy.When the multiple is too low, grafting rate is difficult to reach requirement, influences the bonding force of subsequent adhesive.
Adhesive of the invention also contains antioxidant, stabilizer, initiator, modifying agent (changing other than above-mentioned acid
Property agent) etc. functional additive.These additives can be according to required function as long as not influencing goal of the invention of the invention
Can, it is selected in well known additive.Although the dosage different from of the additive of different function, in general, these function
The content preferably 0.1%~5%, more preferable 0.5~2% of energy property additive can both play corresponding under such content
Function will not generate adverse effect to binder main body.
It is preferred that polymer raw material of the invention is except propylene based compound, as the additive of auxiliary or modifying agent etc.,
Without containing component unstable under any high temperature, to adapt to hot environment.
In addition, it is also preferred that there may be the components for the substance being harmful to the human body at high temperature without containing any, for example, answering
It, should not be containing can produce under high temperature can carcinogenic fluorescence probe or oligomer with phenyl ring when for food packaging.
Polypropylene based material high temperature resistant, chemical property are stablized, and mechanical strength is good, lasted a long time needed for being suitable as,
The higher adhesive of application environment temperature.And in general, purpose for the use environment for meeting the needs of this kind of advantage,
The higher the better for ratio, and in the present invention, preferably graft all uses polypropylene and/or polypropylene elastomer as the sheet being grafted
Body.
The polypropylene is not particularly limited, but from materials, manufacture is convenient and the angle that is easy to get compared with high adherence goes out
Hair, the preferably described polypropylene is homopolypropylene (HPP), copolymer polypropylene (PPR), branched p 0 lypropylene (BPP), polypropylene are elastic
Body (PPE), they can be used alone, and can also be blended to use with two or more.Wherein, it most preferably (is accounted for by principal component of PPE
50 mass % or more more preferably account for 65 mass % or more).Inventors have found that above-mentioned other materials is compared, based on PPE material
Grafting system feed degradation degree controllability is more preferable, and the adhesion level of final product adhesive is more excellent.Thus keep degree of degradation
Requirement can suitably relax, it is more convenient in production.
Above-mentioned several compound-materials are easy to get, and are advantageous for convenient angle from preparing, and for phase
Same purpose, preferably it is more as principal component content, when using homogenous material, the variable parameter being easy to control other than bonding force,
Such as stability, heat resistance etc., practicability is stronger.
As described above, acidic materials used in graft of the invention are not particularly limited, as long as pH < 7 and can
To carry out the organic acidic substances of graft reaction, acid anhydrides also can be used, can also use can release in the reaction
The substance etc. that substance, such as ester etc. of the acidic-group for grafting were originally obtained by organic acid reaction.Specifically, can lift for example,
Acrylic acid, maleic acid, maleic anhydride, methacrylic acid, acrylate, methacrylate, itaconic acid, itaconic anhydride.These
Acidic materials can it is independent a kind use, can also be used in combination with two or more.
The materials of these acidic materials are relatively easy to, and the grafting rate of acquisition is higher, thus is preferred.When the additive amount of acid
When more, the material of the pH partial neutral such as esters can be selected, so that the pH of raw material and product does not have too big variation, can be kept away
Exempt to influence other performances of adhesive.
Acid additive amount be generally polymer 20 weight % hereinafter, it is preferred that 10 weight % hereinafter, more preferable 5 weight % with
Under；Also, it from the angle convenient for measuring effect, is preferably measured with carboxyl contained in acid, i.e., by weight, relatively
The carboxyl amount described in raw material is 0.1~5 weight %, more preferable 0.2~2 weight %, particularly preferred 0.4~1 weight %.
When being measured with carboxyl (when using ester, each ester group can be regarded as 1 carboxyl), it can be counted by following formula
It calculates, i.e., carboxyl-content is equal to:
(carboxyl quantity × carboxyl molecular weight/reaction raw material gross weight contained in sour molal quantity × 1 molecule acid
Amount) × 100%
Wherein, carboxyl molecular weight can approximation be taken as 45 (- COOH, 12+16+16+1=45).
When using acid anhydrides, 1 mole of anhydride group is considered as containing 2 carboxyls, at this point, above formula can be write as:
(acid anhydrides quantity × carboxyl molecular weight/reaction raw material contained in the molal quantity of 2 × acid × 1 molecule acid is total
Weight) × 100%.
As obtained graft, functional group content preferably 0.10~2.0 weight %, more preferable 0.15 weight of lower limit
Measure %, more preferable 0.20 weight %, the upper limit more preferable 1.5 weight %, more preferable 1.2 weight %, more preferable 1.0 weight %.
It is preferred that the graft is added with peroxide initiator in synthesis, the type of the peroxide initiator does not have
Especially limitation can provide the substance of active oxygen atom as long as having-O-O- group in the reaction.Work of the invention
Property oxygen content refers to free radical oxygen atom content/2 that can be generated in graft reaction in peroxide initiator.
Generally preferably with the organic peroxide evocating agent of certain molecular weight, i.e. oxygen atom shared ratio in the molecule
It is smaller.For such selection inorganic active oxygen compound significantly greater relative to active o content in 1 molecule such as hydrogen peroxide,
The severe degree of reaction is easier to control.It reacts, and does not have to for example, whole initiators can be directly mixed in raw material at this time
It slowly instills in batches, is preferred from manufacturing for convenient angle.For example, it is preferable in mass, active oxy group (- O-O-)
Shared ratio (that is, 32 × active oxy group molal quantity/total molecular weight) is less than 30% in 1 molecule, and more preferably less than 15%,
More preferably less than 10%.
For example, it is preferable to initiator can be peroxidating tert-butyl isobutyrate, cyclohexylene two (1,1- dimethyl propyl)
Peroxide, the peroxidating -3,5,5 Trimethylhexanoic acid tert-butyl ester, the peroxidating cis-1 tert-butyl ester, peroxidating diisopropyl
Benzene, 2,5- dimethyl -2,5- two (t-butylperoxy) hexane, di-t-butyl peroxide, 1,1,3,3- tetramethyl butyl peroxide
Change hydrogen.They may be used alone, used in two or more.These above-mentioned initiators can be perfectly suitable for this hair
Bright reaction, and be easy to obtain by commercially available channel.
The additive amount of initiator does not need generally very much, normally in 5 weight ‰ hereinafter, it is preferred that 2.5 ‰ or less weight.From just
In the angle for measuring reaction effect, preferably measured by active o content, that is, by weight, relative to the raw material
The active o content of the peroxide initiator be 0.01~0.5 weight ‰, lower limit preferably 0.02 weight ‰, more preferably
0.04 weight ‰, the upper limit preferably 0.25 weight ‰, more preferable 0.15 weight ‰.
Under such content, graft reaction progress is more smooth, and the bonding force of the adhesive obtained is stablized, simultaneously
Degradation is controllable.Initiator is excessive, the serious degradation of polypropylene of active oxygen, and initiator is very few, graft reaction become difficult to carry out or
Speed is slower, and the site distribution for reacting progress is also not uniform enough, and grafting efficiency is low.
Active o content may be calculated as, i.e., active o content is equal to:
(active oxy group number/2 × active oxy group molecular weight × initiator molal quantity/reaction in 1 initiator molecule
With the total amount of polymer raw material) × 100%
Wherein, active oxy group molecular weight can approximation take 32 (- O-O-, 16+16=32).
[adhesive manufacturing method]
Adhesive of the invention can be manufactured using following method:
For example, can be carried out by following steps.Raw material in following step can be added according to the formula information of table 1
Add, the parameters such as temperature, screw speed of extrusion process are all optionally that technological parameter is to bonding force under the premise of raw material is certain
And without substantial effect.
(i) raw material premix are premixed sour modifying agent and initiator and polymer raw material using mixing machine, in mixed process
In, they can be evenly coated on polymer raw material.
(ii) above-mentioned premix material is added in the double screw extruder that 30mm draw ratio is 56 and reacts by reactive extrursion
Grafting.
(iii) discharge shaping, for example, (this step can be according to final products for check rod, cooling, drying, pelletizing, packaging etc.
The requirement of form suitably select).
The graft can be used as intermediate and directly be saved, transported, be traded, and be formulated as gluing before actual use again
Mixture specifically can carry out by the following method blending dilution:
(a) it premixes, is uniformly mixed above-mentioned graft and newly added polymer raw material with mixing machine, specific ingredient can
It is prepared like that according to table 1.
(b) blending extrusion above-mentioned material is added in the double screw extruder that 30mm draw ratio is 40, screw speed
400rpm, rate of feeding 20kg/h, plasticizing set temperature are 180 DEG C.
(c) discharge shaping, for example, (this step can be according to final products for check rod, cooling, drying, pelletizing, packaging etc.
The requirement of form suitably selects).
[binder performance test]
(1) melting means measures
The present invention utilizes prosperous XNR-400B melting means instrument test material melt index.The original raw material ginseng given except supplier
Other than number, the identification of all raw materials and product detection are implemented according to testing standard ISO 1133.
(2) aluminium flake/adhesive alpha-olefin inter/aluminium flake composite construction preparation
The present invention prepares aluminium flake/adhesive alpha-olefin inter/aluminium flake composite construction using vulcanizing press.The present invention uses
The aluminium flake of 0.2mm thickness prepares composite construction for follow-up test.Sample preparation temperature is 230 DEG C, pressing time 5min.Aluminium
Piece/polypropylene binders/aluminium flake composite construction is having a size of 200mm × 25mm × 2mm.
(3) 180 ° of peel strength tests
The present invention tests aluminium flake/poly- third using the MZ-9000 type universal testing machine of wise electronics limited liability company
Alkenyl adhesive/180 ° of aluminium flake composite construction peel strength.Its peeling rate is 100mm/min.
(4) preparation of adhesive alpha-olefin inter film
The present invention prepares test polypropylene based membrane using the R140-Y2:2-17-M1 inflation film manufacturing machine of Bo Ruijie company, blows
Each warm area set temperature of film machine is 180 DEG C, is obtained with a thickness of the adhesive alpha-olefin inter film of 0.2mm thickness.
(5) PA film/adhesive alpha-olefin inter/PP film composite construction preparation
The present invention prepares PA film/adhesive alpha-olefin inter/PP film composite construction, final test sample knot using heat-sealing instrument
Structure is paper/adhesive alpha-olefin inter/PA film/adhesive alpha-olefin inter/PP film/adhesive alpha-olefin inter/paper.The present invention uses
The A4 paper of 70g, the face PA of 0.1mm PA/PP packaging bag and the face PP are used for follow-up test as PA and PP film preparation composite construction.
Sample preparation temperature is 220 DEG C, and the heat-sealing time is 9s, and heat-sealing pressure is 0.2MPa.PA film/adhesive alpha-olefin inter/PP film is multiple
Conjunction structure size is 100mm × 10mm × 0.65mm.
(6) aluminium foil/adhesive alpha-olefin inter/PP film composite construction preparation
The present invention prepares aluminium foil/adhesive alpha-olefin inter/PP film composite construction, final test sample knot using heat-sealing instrument
Structure is paper/adhesive alpha-olefin inter/aluminium foil/adhesive alpha-olefin inter/PP film/adhesive alpha-olefin inter/paper.The present invention uses
The A4 paper of 70g, makes 0.1mmPP film by oneself as PP film preparation composite construction for follow-up test at 0.1mm aluminium foil.Sample preparation temperature
Degree is 220 DEG C, and the heat-sealing time is 12s, and heat-sealing pressure is 0.2MPa.PA film/adhesive alpha-olefin inter/PP film composite construction size
For 100mm × 10mm × 0.5mm.
(7) heat-sealing structure peel strength test
The present invention tests PA film/poly- third using the MZ-9000 type universal testing machine of wise electronics limited liability company
Alkenyl adhesive/PP film composite construction and aluminium foil/adhesive alpha-olefin inter/PP film composite construction peel strength.Its peeling rate
For 100mm/min.
Test result is as shown in table 2.
1 adhesive formula of table
1 adhesive formula (Continued) of table
2 binder performance of table
2 binder performance (Continued) of table
In upper table:
Al/tie/PPR: aluminium foil layer/adhesive phase/heat-sealing polypropylene layer
PA/tie/PPR: aramid layer/adhesive phase/heat-sealing polypropylene layer
Al/tie/Al: aluminium flake layer/adhesive phase/aluminium flake layer
3 pp material information of table
4 polyene hydrocarbons and their derivates raw material information of table
4 polyene hydrocarbons and their derivates raw material information (Continued) of table
5 graft manner of formulation of table
Claims (9)
1. adhesive alpha-olefin inter characterized by comprising
Polypropylene-based graft object,
Non-grafted polypropylene,
The polyolefin or polyolefin derivative object different from above-mentioned the two；
With the total amount of above-mentioned three kinds of components be 100 mass parts when, wherein the content of the Polypropylene-based graft object be a mass parts,
The non-grafted polyacrylic content is that the content of b mass parts, the polyolefin or polyolefin derivative object is c mass parts, is met
Following relationship:
2 < a < 40,
-30<a-0.435b+0.202c<10；
The Polypropylene-based graft object be acidic materials are grafted on polypropylene elastomer or polypropylene and polypropylene elasticity
Obtained from body.
2. adhesive alpha-olefin inter according to claim 1, which is characterized in that with the total amount of above-mentioned three kinds of components for 100
When mass parts, wherein the content of the Polypropylene-based graft object is a mass parts, the non-grafted polyacrylic content is b mass
The content of part, the polyolefin or polyolefin derivative object is c mass parts, meets following relationship: 10 < a < 25.
3. adhesive alpha-olefin inter according to claim 2, which is characterized in that with the total amount of above-mentioned three kinds of components for 100
When mass parts, wherein the content of the Polypropylene-based graft object is a mass parts, the non-grafted polyacrylic content is b mass
The content of part, the polyolefin or polyolefin derivative object is c mass parts, meets following relationship:
B/a=2~10,
C/a=0.5~3.
4. adhesive alpha-olefin inter according to claim 3, which is characterized in that it is described in mass, with above-mentioned three kinds of groups
When the total amount divided is 100 mass parts, wherein the content of the Polypropylene-based graft object is a mass parts, the non-grafted polypropylene
Content be the contents of b mass parts, the polyolefin or polyolefin derivative object be c mass parts, meet following relationship: c/b=
0.1~0.6.
5. the adhesive alpha-olefin inter recorded according to claim 1~any one of 4, which is characterized in that the polypropylene-base connects
Branch object be selected from group composed by homopolypropylene, copolymer polypropylene, branched p 0 lypropylene any one kind or two or more and
The graft of the mixture of polypropylene elastomer.
6. adhesive alpha-olefin inter according to claim 5, which is characterized in that the acidic materials are acrylic acid, Malaysia
Acid, maleic anhydride, methacrylic acid, acrylate, methacrylate, itaconic acid, any a kind or 2 kinds in itaconic anhydride
Above mixture.
7. the adhesive alpha-olefin inter recorded according to claim 1~any one of 4, which is characterized in that the polyolefin is poly-
Alkene derivatives are ethylene-vinyl acetate copolymer, hydrogenated styrene-butadiene-styrene block copolymers, styrene-fourth
Styrene block copolymer, polypropylene elastomer, polyethylene, olefin block copolymers, styrene-isoprene-benzene second
Alkene block copolymer, high impact polystyrene, any one kind or two or more mixture in general purpose polystyrene.
8. the adhesive alpha-olefin inter recorded according to claim 1~any one of 4, which is characterized in that described non-grafted poly- third
Alkene is any one kind or two or more mixture in homopolypropylene, copolymer polypropylene and branched p 0 lypropylene.
9. the adhesive alpha-olefin inter recorded according to claim 1~any one of 4, which is characterized in that described adhesive is to aluminium
The bonding force of foil is 1.0N/mm or more, and the bonding force to PA membrane is 1.0N/mm or more, and the bonding force to aluminium flake is 4.0N/
Mm or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710414322.4A CN107033810B (en) | 2017-06-05 | 2017-06-05 | Adhesive alpha-olefin inter |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710414322.4A CN107033810B (en) | 2017-06-05 | 2017-06-05 | Adhesive alpha-olefin inter |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107033810A CN107033810A (en) | 2017-08-11 |
| CN107033810B true CN107033810B (en) | 2019-01-04 |
Family
ID=59540571
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710414322.4A Active CN107033810B (en) | 2017-06-05 | 2017-06-05 | Adhesive alpha-olefin inter |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107033810B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3839002A1 (en) * | 2019-12-20 | 2021-06-23 | Bostik Sa | Hot-melt adhesive composition |
| CN114045127B (en) * | 2021-11-24 | 2023-04-21 | 合诚技术股份有限公司 | Adhesive resin for soft package lithium ion battery aluminum plastic film, and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104371597B (en) * | 2014-12-02 | 2017-11-07 | 河源市普立隆新材料科技有限公司 | A kind of preparation method of multi-layer co-extruded barrier package polypropylene adhering resin |
-
2017
- 2017-06-05 CN CN201710414322.4A patent/CN107033810B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN107033810A (en) | 2017-08-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI335349B (en) | Aqueous dispersions | |
| CN101765613B (en) | Improved rheology-modified grafts and adhesive blends | |
| CN103118872B (en) | For improvement of the graft composition of articulamentum | |
| US10385242B2 (en) | Adhesive compositions containing modified ethylene-based polymers | |
| JP2000507283A (en) | Olefin polymer-containing adhesive | |
| KR101915764B1 (en) | Olefin-based polymer compositions and articles prepared therefrom | |
| US10450484B2 (en) | Adhesive compositions containing functionalized ethylene/alpha-olefin interpolymers and rosin-based tackifiers | |
| CN102803356A (en) | Composition for stretch film | |
| CN107033810B (en) | Adhesive alpha-olefin inter | |
| ITMI950478A1 (en) | COMPOSITION OF CO-EXTRUSION BINDER AND CO-EXTRUDED MULTILAYER COMPOSITE IN WHICH SAID COMPOSITION IS USED AS LAYER | |
| CN108949046B (en) | EVA hot melt adhesive film for wall cloth and preparation method thereof | |
| JP2011236410A (en) | Plant-based resin pellet, method for producing the same, and injection molding machine by using the plant-based resin material | |
| CN104327347A (en) | High-molecular bonding resin used for non-PVC medical transfusion bag and preparation method thereof | |
| US20080039583A1 (en) | Adhesive composition | |
| WO2009033465A2 (en) | Method for producing carboxylated ethylene polymer blends | |
| US20180346707A1 (en) | Adhesive Formulations for Fabric/POE Adhesion | |
| CN108893068A (en) | A kind of wall paper halogen-free flameproof EVA hot-melt adhesive film and preparation method thereof | |
| CN106085021B (en) | Alloy-type coating material and preparation method thereof | |
| CN106905892A (en) | A kind of adhesive based on non-polar, polyolefin resin | |
| CN109880445A (en) | A kind of high bonding force polyethylene powder coating and its preparation method and application | |
| CN102234495A (en) | Water-dispersed pressure-sensitive adhesive composition and method of production | |
| CN106905491B (en) | Polypropylene-base acid modified grafts and adhesive containing the graft | |
| CN104419009B (en) | A kind of SEBS graft copolymers and preparation method thereof and its purposes | |
| US20100197834A1 (en) | Resin composition blended with starchy material | |
| EP2902461B1 (en) | Hot melt pressure sensitive adhesive |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Polypropylene based adhesive Effective date of registration: 20220311 Granted publication date: 20190104 Pledgee: Xiamen Jinyuan Financing Guarantee Co.,Ltd. Pledgor: XIAMEN NEIJIAHU NEW MATERIAL TECHNOLOGY CO.,LTD. Registration number: Y2022980002471 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |