CN101864025B - Preparation method of polyacrylate microgel emulsion and application thereof - Google Patents
Preparation method of polyacrylate microgel emulsion and application thereof Download PDFInfo
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- CN101864025B CN101864025B CN2010102044612A CN201010204461A CN101864025B CN 101864025 B CN101864025 B CN 101864025B CN 2010102044612 A CN2010102044612 A CN 2010102044612A CN 201010204461 A CN201010204461 A CN 201010204461A CN 101864025 B CN101864025 B CN 101864025B
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Abstract
The invention provides a method for synthetizing polyacrylate microgel emulsion in a soap-free emulsion polymerization mode, which comprises the following processes: (1) pre-emulsification: mixing a variety of monomers for emulsification to prepare pre-emulsified liquid; (2) seed polymerization: carrying out a polymerization reaction on a small amount of pre-emulsified liquid after the activation of an initiator to prepare seed solution; (3) polymerization: continuing to drip the pre-emulsified liquid in the seed solution to prepare microgel; and (4) ammonification: dripping hartshorn to regulate PH to prepare the polyacrylate microgel emulsion. The process is simple, the condition is easy to control, the emulsion is easy for scale production and can be used as the main constituent of aqueous adhesive used for flexible package plastic-plastic composition, and the prepared polyacrylate microgel aqueous adhesive has strong binding power on base materials, is waterproof, resists heat, is environmental-friendly, and has high drying speed.
Description
Technical field
The present invention relates to technical field of macromolecules, relate to a kind of preparation method of polyacrylate microgel emulsion especially and be applied to package compound and use with sizing agent.
Background technology
The enhancing of Along with people's environmental consciousness and to the attention of food product pack safety also proposes increasingly high standard and requirement to package compound with tackiness agent.In the sticker of China's food composite soft packaging bag usefulness, the solvent borne polyurethane tackiness agent occupies more than 90%, and solvent-free and water-based compound binding agent accounts for less than 10%.There is dissolvent residual harm in Solvent Adhesive; The no-solvent type compound binding agent can not satisfy the requirement of poach crane high temperature steaming; And need special equipment and aqueous binders can directly apply to dry complex equipment; And can reach all performance requriementss of no-solvent type sticker, so aqueous binder replaces the direction that Solvent Adhesive will be the compound sizing agent development of following food product pack.
Emulsifier-free emulsion polymerization is claimed emulsifier-free emulsion polymerization again, and it refers in polymerization process, not add fully or only add the emulsion polymerization process of micro-emulsifying agent (its concentration is less than etherealness micellar concentration CMC).Emulsifier-free emulsion polymerization is removed the aftertreatment of removing emulsifying agent from, and the polymer emulsion surface cleaning, and the particle diameter monodispersity of micelle is good, and particle is big.It mainly is to be determined by the surfactivity oligopolymer that the emulsion latex particle gets stable, improves polymkeric substance and gets polarity, makes particle surface and aqueous phase interface interact, and reduces the interface and gets the Cibbs free energy, can improve the stability of particle.
Microgel is a kind of polymer particle with intramolecular crosslinking structure, but stable dispersion is in organic solvent or water.The particle diameter of microgel is 1nm～1 μ m, and swelling to a certain degree can take place in liquid phase.In polymerization process, micro-gel surface or inner residual a large amount of reactive groups (like two keys, carboxyl, epoxy group(ing) etc.), these groups under proper condition with other monomers or polymkeric substance generation crosslinking reaction, produce network polymer.This type of microgel is referred to as reactive micro-gel.
Reactive emulsifier generally all contains two keys, can participate in polyreaction, and after polymerization process or polyreaction, surfactant molecule can be strongly bound on the latex particle.Polymerisable emulsifying agent is divided into anionic polymerisable emulsifier, cationic polymerizable emulsifying agent, non-ionic type polymerisable emulsifier and both sexes polymerisable emulsifier by the type of its hydrophilic group.
Number of patent application: 200610118725 disclose a kind of preparation method and application of reactive polyacrylate microgel.This method comprises that (1) is synthetic: compound emulsifying agent adds monomer, stirs, and emulsification in advance adds initiator, makes translucent micro polymer latex; (2) ammonification: stir dropping ammonia solution down, regulate p H value 7～8, make the emulsion of transparent clear.Its application is above-mentioned microgel emulsion to be added process the compound fabric pigment printing binding agent in the binding agent for pigment printing and other raw material is made into printing paste together.Coagulate the aqueous assembly glue that compound usefulness is moulded in inapplicable soft packaging but this reactive polyacrylate is little.
According to bibliographical information, domestic existing Donghua University, South China Science & Engineering University are coated with big duckweed study group, Cao of University Of Tianjin with research units such as beautiful study group all in the work of carrying out this respect.They mainly concentrate on the preparation method and the sign of reactive micro-gel, and the preparation method who has reported comprises conventional emulsion polymerization, core-shell emulsion polymerization, and micro-emulsion polymerization rarely has the report of emulsifier-free emulsion polymerization mode.The applied research of reactive micro-gel emulsion seldom, the scope of application only limit to paint field with the weaving rubber cement, also do not see at package printing industry use adhesive area and use.
In soft packaging industry, the compound traditional tackiness agent that uses of composite package dry method is solvent-based adhesive, must be through the dry Ex-all of drying tunnel solvent wherein; So that follow-up applying processing; Produce quality products, therefore in recombination process, have high amounts of solvents to get rid of; Form the huge source of pollution that pollute operation workshop and surrounding enviroment, totally unfavorable to workers'health and environmental protection work; The use of solvent, the hidden danger of aspects such as burning in addition, blast and so on, becomes a big defective of its application, also becomes industry extensive concern and one of difficulty of making great efforts to capture.The Application and Development of aqueous binder for solving the compound existing for a long time safety of dry method, environmental issue, provides an excellent approach.
At present aqueous binder at aspect of performance (like bonding force, thermotolerance, water-fast, solvent resistance and printing adaptability) to different substrate materials also far away less than Solvent Adhesive, especially boiling resistance can and rate of drying aspect.To this, the direction of research mainly is to set about from the polymerization technique aspect of emulsion both at home and abroad.
Summary of the invention
The present invention adopts the emulsifier-free emulsion polymerization mode to synthesize polyacrylate microgel emulsion, utilizes its reactive group to improve the bonding force to various base materials; Utilize the mechanical propertys such as hardness and tensile strength of high crosslink density and no soap characteristic raising glued membrane, improve thermotolerance, water tolerance and the solvent resistance of glued membrane; Utilize the characteristic of its high-solid lower-viscosity to improve rate of drying; Thereby it is slow to solve water-and acrylate emulsion adhesive inherent rate of drying; The stripping strength of composite prod is low, and defective such as heat-resisting, resistance to medium difference reaches the technological difficulties of the performance of solvent borne polyurethane tackiness agent.
The present invention solves the problems of the technologies described above the technical scheme that is adopted to be:
A kind of preparation method of polyacrylate microgel emulsion, it may further comprise the steps:
1, in advance emulsification: take by weighing 200～250 parts of deionized waters, with the deionized water total amount 1/3～2/3,100 parts of (flexible monomers of long-chain: Bing Xisuandingzhi of mix monomer; Functional monomer: the monomer of Hydroxyethyl acrylate, vinylformic acid, epoxy group(ing); Polyfunctionality monomer: Tri Ethyleneglycol dimethacrylate or Vinylstyrene), reactive emulsifier adds in the emulsification still, high-speed stirring is carried out preparatory emulsification 10～30min, pre-emulsion.
2, seeding polymerization: in reaction kettle, add the residue deionized water 20%～40%, nonionic emulsifying agent; Stirring heating; Temperature reaches 60 ℃, adds initiator a, when temperature reaches 75 ℃; Drip the described pre-emulsion of 20%～40% step 1 fast, and at 75～85 ℃ of insulation reaction 30min.
3, polyreaction: after seeding polymerization was accomplished, beginning dripped described pre-emulsion of remaining step 1 and initiator b simultaneously, and temperature of reaction is controlled at 80～90 ℃, insulation reaction 30～60min, and discharging is filtered in cooling, makes translucent micro polymer latex.
4, ammonification: be cooled to 60～70 ℃, dropping ammonia solution under the violent stirring, regulating pH value is 7～8, makes polyacrylate microgel emulsion.
The microgel emulsion that makes according to the preparation method of above-mentioned polyacrylate microgel emulsion is polymerized by following parts by weight of raw materials component:
100 parts of mix monomers
1～1.2 part of emulsifying agent
0.2～0.4 part of radical initiator
200～250 parts of deionized waters
0～0.04 part of PH regulator
Said mix monomer comprises: the flexible monomer of long-chain, functional monomer, polyfunctionality monomer, and its parts by weight of raw materials component is:
A, the flexible monomer of long-chain
75 parts of Bing Xisuandingzhis
B, functional monomer
7.2～17 parts of Hydroxyethyl acrylates
1.2～2.4 parts in vinylformic acid
0.3～0.8 part of epoxy-based functional monomer
C polyfunctionality monomer
Vinylstyrene
Or 0.1～0.4 part of Tri Ethyleneglycol dimethacrylate
Said emulsifying agent comprises:
0.1～0.2 part of reactive emulsifier,
0.1 part of nonionic emulsifier;
Said radical initiator comprises: initiator a, initiator b, and its material component is:
Initiator a
K
2S
2O
80.12 part,
H
26 parts of O
Initiator b
0.15 part of tertbutyl peroxide
H
25 parts of O
When initiator amount was 0.2～0.4, the acrylic acid esters co-polymer emulsion of preparation was blue phase, the emulsion granularity is little, and the good stability of emulsion.The adding method of initiator: when initiator added the people to pre-emulsion, monomer reaction was more complete, so transformation efficiency is high; Add initiator on this basis again one time, unreacted residual monomer is reacted, transformation efficiency further improves.APS thermolysis in water produces small amount of H SO
4 -, this ion further is ionized into H
+And SO
4 2-Ion, thereby along with the carrying out of polyreaction, system pH reduces, the change of pH value can have influence on the emulsifying effectiveness of emulsifying agent and the efficiency of initiation of initiator again, thus big or small and distribution exerts an influence to micelle.Therefore adopt and add PH regulator ammoniacal liquor.
Said PH regulator is an ammoniacal liquor for 0～0.04 part.
A kind of application of polyacrylate microgel emulsion is to be staple with above-mentioned microgel emulsion, prepares soft packaging and moulds compound use tackiness agent.
The beneficial effect of the invention:
1, adopt the reactive surfactant emulsifying agent to reduce electrolytical content in the emulsion, reduce that foamy forms and product in impurity, improved the performance of emulsion simultaneously at aspect such as water-fast.
2, adopt the synthetic polyacrylate microgel emulsion of no soap emulsifier-free emulsion polymerization mode to be, the preparation emulsion, earlier synthetic seed emulsion continues to add the method for emulsion again, improves turnover ratio, can make high-solid lower-viscosity and get microgel emulsion.
3, the reactive micro-gel Vestolen PP 7052 ester emulsion that the present invention is prepared is added to soft packaging and moulds in the aqueous binders of compound usefulness, can improve the rate of drying of aqueous binders, to the adhesiveproperties and the boiling resistance of base material.
4, microgel emulsion of the present invention as the technical performance index that the water-based sizing agent of staple preparation reaches is: outward appearance: milky white liquid; PH value: 7.5～8.5; Solid content: 41.0～43.0%; Viscosity: 12.5～13.5 seconds (being coated with 4 glasss 25 ℃); Quality guaranteed period:＞6 months; Freeze-thaw stability: through 5 times; Stripping strength:＞1.2N/15mm (VMPET or VMCPP/BOPP or PET);＞1.8N/15mm (CPP/BOPP or PET);＞10N/15mm (heat-sealing).
Below in conjunction with embodiment, the present invention is further specified.
Specific embodiment
Embodiment 1
Present embodiment provides a kind of preparation method of polyacrylate microgel emulsion, and it may further comprise the steps:
1, emulsification in advance: take by weighing 200～250 parts of deionized waters; With the deionized water total amount 1/3～2/3,100 parts of mix monomers (the flexible monomers of long-chain: 75 parts of Bing Xisuandingzhis; 0.1 part of Vinylstyrene), 0.1 part of reactive emulsifier adds in the emulsification still high-speed stirring functional monomer: 0.3 part of the monomer of 7.2 parts of Hydroxyethyl acrylates, 1.2 parts in vinylformic acid, epoxy group(ing), polyfunctionality monomer:; Carry out preparatory emulsification 10～30min, get emulsion.
2, seeding polymerization: in reaction kettle, add the residue deionized water 20%～40%, 0.1 part of nonionic emulsifying agent, stirring heating, temperature reach 60 ℃, add initiator a (component: K
2S
2O
80.12 part, H
2O6 part) reach 75 ℃ when temperature, drip the described pre-emulsion of 20%～40% step 1 fast, and at 75～85 ℃ of insulation reaction 30min.
3, polyreaction: after seeding polymerization was accomplished, beginning dripped the described pre-emulsion of remaining step 1 and initiator b (0.15 part of tertbutyl peroxide, H simultaneously
25 parts of O), temperature of reaction is controlled at 80～90 ℃, insulation reaction 30～60min, and discharging is filtered in cooling, makes translucent micro polymer latex.
4, ammonification: be cooled to 60～70 ℃, dropping ammonia solution is 0.01 part under the violent stirring, regulates pH value to 7～8, makes polyacrylate microgel emulsion.
The microgel of above-mentioned preparation is added soft packaging to be moulded in the compound binding agent dispersed with stirring and processes the aqueous binders that compound usefulness is moulded in soft packaging.
The reactive micro-gel Vestolen PP 7052 ester emulsion high-solid lower-viscosity that present embodiment makes; Good stability; It is joined soft packaging mould adhesive property and the boiling resistance that improves assembly glue in the aqueous binders of compound usefulness, also improved rate of drying, the technical indicator that product of the present invention reaches is following:
Embodiment 2
Present embodiment provides the preparation method of polyacrylate microgel emulsion, and its manufacturing step and embodiment 1 are basic identical, and its difference is: the raw material of the polyacrylate microgel emulsion that present embodiment makes consists of:
75 parts of Bing Xisuandingzhis
10 parts of Hydroxyethyl acrylates
1.5 parts in vinylformic acid
0.6 part of epoxy-based functional monomer
2 parts of Vinylstyrenes
0.15 part of reactive emulsifier
0.1 part of nonionic emulsifier
220 parts of deionized waters
0.02 part of PH regulator
Said radical initiator comprises that the material component of initiator a, initiator b is:
K
2S
2O
80.15 part,
H
27.5 parts of O
Initiator b
0.15 part of tertbutyl peroxide
H
25 parts of O
The present embodiment effect is identical with embodiment 1.
Embodiment 3
Present embodiment provides the preparation method of polyacrylate microgel emulsion, and its manufacturing step and embodiment 1 are basic identical, and its difference is: the raw material of the polyacrylate microgel emulsion that present embodiment makes consists of:
75 parts of Bing Xisuandingzhis
15 parts of Hydroxyethyl acrylates
2.4 parts in vinylformic acid
0.6 part of epoxy-based functional monomer
0.7 part of Vinylstyrene
0.15 part of reactive emulsifier
0.1 part of nonionic emulsifier
250 parts of deionized waters
0.02 part of PH regulator
Said radical initiator comprises that the material component of initiator a, initiator b is:
K
2S
2O
80.15 part,
H
27.5 parts of O
Initiator b
0.15 part of tertbutyl peroxide
H
25 parts of O
The present embodiment effect is identical with embodiment 1.
Embodiment 4
Present embodiment provides the preparation method of polyacrylate microgel emulsion, and its manufacturing step and embodiment 1 are basic identical, and its difference is: the raw material of the polyacrylate microgel emulsion that present embodiment makes consists of:
75 parts of Bing Xisuandingzhis
15 parts of Hydroxyethyl acrylates
1.5 parts in vinylformic acid
0.6 part of epoxy-based functional monomer
0.2 part of Vinylstyrene
0.15 part of reactive emulsifier
0.1 part of nonionic emulsifier
230 parts of deionized waters
0.02 part of PH regulator
Said radical initiator comprises that the material component of initiator a, initiator b is:
K
2S
2O
80.15 part
H
27.5 parts of O
Initiator b
0.15 part of tertbutyl peroxide
H
25 parts of O
The present embodiment effect is identical with embodiment 1.
Embodiment 5
Present embodiment provides the preparation method of polyacrylate microgel emulsion, and its manufacturing step and embodiment 1 are basic identical, and its difference is: the raw material of the polyacrylate microgel emulsion that present embodiment makes consists of:
75 parts of Bing Xisuandingzhis
15 parts of Hydroxyethyl acrylates
2 parts in vinylformic acid
0.3 part of epoxy-based functional monomer
0.3 part of Vinylstyrene
0.15 part of reactive emulsifier
0.1 part of nonionic emulsifier
250 parts of deionized waters
0.01 part of PH regulator
Said radical initiator comprises that the material component of initiator a, initiator b is:
K
2S
2O
80.15 part,
H
27.5 parts of O
Initiator b
0.15 part of tertbutyl peroxide
H
25 parts of O
The present embodiment effect is identical with embodiment 1.
The present invention is not limited to the foregoing description, and every all embodiments that are equal to that can realize the object of the invention are all within protection scope of the present invention.
Claims (2)
1. the preparation method of a polyacrylate microgel emulsion is characterized in that, it may further comprise the steps:
1) in advance emulsification: take by weighing 200～250 parts of deionized waters, with the deionized water total amount 1/3～2/3,100 parts of mix monomers, reactive emulsifier add in the emulsification still for 0.1～0.2 part, high-speed stirring is carried out preparatory emulsification 10～30min, pre-emulsion;
2) seeding polymerization: in reaction kettle, add the said deionized water residual content of step 1) 1/5～2/5,0.1 part of nonionic emulsifying agent; Stirring heating; Temperature reaches 60 ℃, adds initiator a, when temperature reaches 75 ℃; Drip the described pre-emulsion of 1/5～2/5 step 1) fast, and at 75～85 ℃ of insulation reaction 30min;
3) polyreaction: after seeding polymerization was accomplished, beginning dripped described pre-emulsion of remaining step 1) and initiator b simultaneously, and temperature of reaction is controlled at 80～90 ℃, insulation reaction 30～60min, and discharging is filtered in cooling, makes translucent micro polymer latex;
4) ammonification: be cooled to 60～70 ℃, dropping ammonia solution is 0～0.04 part under the violent stirring, regulates pH value to 7～8, makes polyacrylate microgel emulsion;
The described mix monomer of step 1) comprises the flexible monomer of long-chain, functional monomer, polyfunctionality monomer, and its parts by weight of raw materials component is:
The flexible monomer of a long-chain
75 parts of Bing Xisuandingzhis
The b functional monomer
7.2～17 parts of Hydroxyethyl acrylates
1.2～2.4 parts in vinylformic acid
0.3～0.8 part of epoxy-based functional monomer
C polyfunctionality monomer
0.1～0.4 part of Vinylstyrene
Step 2) the parts by weight of raw materials component of said initiator is:
Initiator a
K
2S
2O
80.12 part,
H
26 parts of O
The parts by weight of raw materials component of the said initiator of step 3) is:
Initiator b
0.15 part of tertbutyl peroxide
H
25 parts of O.
2. application according to the said polyacrylate microgel emulsion of claim 1 is with polyacrylate microgel emulsion, adds soft packaging and moulds dispersed with stirring in the compound binding agent, and the aqueous binders of compound usefulness is moulded in the preparation soft packaging.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102044612A CN101864025B (en) | 2010-06-21 | 2010-06-21 | Preparation method of polyacrylate microgel emulsion and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102044612A CN101864025B (en) | 2010-06-21 | 2010-06-21 | Preparation method of polyacrylate microgel emulsion and application thereof |
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| CN101864025A CN101864025A (en) | 2010-10-20 |
| CN101864025B true CN101864025B (en) | 2012-07-04 |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103387806B (en) * | 2013-07-18 | 2015-09-09 | 东莞市芙蓉化工有限公司 | A kind of have pressure-sensitive polyacrylate emulsion glue of reactive micro-gel structure and preparation method thereof |
| CN103980412B (en) * | 2014-05-15 | 2016-05-25 | 中国建筑材料科学研究总院 | A kind of preparation method of nano core-shell structure efficient molecular sieve drier |
| CN104774287B (en) * | 2015-03-12 | 2017-04-26 | 杭州海维特化工科技有限公司 | Polyacrylate emulsion microgel and preparation method thereof |
| CN106147672B (en) * | 2015-04-07 | 2018-06-19 | 宏峰行化工(深圳)有限公司 | It is a kind of to be used to moulding/moulding compound aqueous polyurethane acrylate adhesive and preparation method thereof |
| CN106147659B (en) * | 2015-04-09 | 2018-06-19 | 宏峰行化工(深圳)有限公司 | It is a kind of to be used to moulding/moulding compound phosphoric acrylic ester adhesive and preparation method thereof |
| CN105669914B (en) * | 2016-03-23 | 2018-12-28 | 广州天赐高新材料股份有限公司 | A kind of freeze-thaw stable type acrylate polymer emulsion and preparation method thereof |
| CN106349423B (en) * | 2016-08-24 | 2018-04-10 | 江苏永阳新材料科技有限公司 | A kind of water-and acrylate ceramic tile bond and its preparation method and application |
| CN107459603B (en) * | 2017-08-30 | 2020-03-27 | 佛山市高明同德化工有限公司 | Hydroxy-rich micro-gel emulsion and preparation method thereof |
| CN110305243B (en) * | 2019-07-02 | 2021-08-24 | 南京工业大学 | Preparation method of high-solid-content monodisperse pure acrylic colloid emulsion |
| CN113562284A (en) * | 2021-07-23 | 2021-10-29 | 上海紫丹食品包装印刷有限公司 | Food-grade packaging paper barrel |
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| CN101168650A (en) * | 2006-10-23 | 2008-04-30 | 吴达文 | Single-component self-crosslink emulsion adhesive for dry type composite film and preparation method thereof |
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