CN106349422A - Water-soluble acrylate resin and synthesis method thereof - Google Patents

Water-soluble acrylate resin and synthesis method thereof Download PDF

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Publication number
CN106349422A
CN106349422A CN201610800277.1A CN201610800277A CN106349422A CN 106349422 A CN106349422 A CN 106349422A CN 201610800277 A CN201610800277 A CN 201610800277A CN 106349422 A CN106349422 A CN 106349422A
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Prior art keywords
parts
acrylate resin
water
water soluble
soluble acrylate
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Pending
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CN201610800277.1A
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Chinese (zh)
Inventor
李翔
刘勇
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JIANGSU LIWENJIA CHEMICAL Co Ltd
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JIANGSU LIWENJIA CHEMICAL Co Ltd
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Priority to CN201610800277.1A priority Critical patent/CN106349422A/en
Publication of CN106349422A publication Critical patent/CN106349422A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers 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
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/12Esters of monohydric alcohols or phenols
    • C08F220/14Methyl esters, e.g. methyl (meth)acrylate
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04Homopolymers or copolymers of esters
    • C09D133/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10Homopolymers or copolymers of methacrylic acid esters
    • C09D133/12Homopolymers or copolymers of methyl methacrylate

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention discloses a water-soluble acrylate resin and a synthesis method thereof. The water-soluble acrylate resin is prepared from, by mass, 20-30 parts of methyl methacrylate, 0-10 parts of styrene, 0-10 parts of butyl acrylate, 0-10 parts of 2-ethylhexyl acrylate, 0-15 parts of methacrylic acid, 0-15 parts of acrylic acid, 0-3 parts of hydroxyethyl methylacrylate, 0-3 parts of hydroxy-propyl acrylate, 1-3 parts of benzoyl peroxide, 35-45 parts of isopropanol, 10-15 parts of ammonium hydroxide and 15-40 parts of deionized water. The invention further discloses application of the water-soluble acrylate resin to preparation of waterborne wood paint. The waterborne wood paint prepared from the water-soluble acrylate resin is excellent in coating physical performance, high in hardness and gloss and good in fullness. The water-soluble acrylate resin has the advantages of safety in use, resource and energy saving, environmental pollution and public hazard reduction and the like.

Description

A kind of water soluble acrylate resin and its synthetic method
Technical field
The invention belongs to technical field of aqueous paint is and in particular to a kind of water soluble acrylate resin and its synthesis side Method.
Background technology
Since the nineties in 20th century, solvent based coating, paint and adhesives industry are by high pollution, high energy consumption, pole Degree depends on the traditional category of petroleum industry product to be increasingly turned to environmental friendliness, resource and energy conservation type product, various environmental protection Type kind continues to bring out, and wherein water paint and aqueous binder industry achieve significant progress.Water paint has price Low, use safety, save resources and the energy, reduce the advantages of environmental pollution and public hazards, thus become current development coating work The Main way of industry.Water soluble acrylic acid olefine resin coating is pollution-free coating with fastest developing speed in water paint, that kind is most.
With the raising of social progress and living standards of the people, waterborne polymeric product also will welcome the spring of fast development My god.Realization paint, coating, the key of binding agent Water-borne modification are how to realize the Water-borne modification of polymer, and the performance pair of polymer The performance of waterborne polymeric product (as aqueous anticorrosion paint, aqueous ink, aqueous binder, building coating, aqueous woodware paint etc.) rises To conclusive effect.
Content of the invention
It is an object of the invention to provide a kind of water soluble acrylate resin and its synthetic method, it is that water paint industry carries For the brand-new high-performance water-based film-forming resin of a class, promote product renewal and the technological progress of related industry.
For achieving the above object, the present invention is achieved by the following technical solutions:
A kind of water soluble acrylate resin is it is characterised in that be prepared from by the raw material of following mass fraction: methacrylic acid Methyl ester 20-30 part, styrene 0-10 part, butyl acrylate 0-10 part, Isooctyl acrylate monomer 0-10 part, methacrylic acid 0-15 Part, acrylic acid 0-15 part, hydroxyethyl methylacrylate 0-3 part, Hydroxypropyl acrylate 0-3 part, benzoyl peroxide 1-3 part is different Propanol 35-45 part, ammonia 10-15 part, deionized water 15-40 part.
The mass concentration of described ammonia is 25%.
Further, described water soluble acrylate resin, is preferably prepared from by the raw material of following mass fraction: methyl 30 parts of acrylic acid methyl ester., 5 parts of butyl acrylate, 5 parts of methacrylic acid, 5 parts of acrylic acid, 1 part of Hydroxypropyl acrylate, benzoyl peroxide 2 parts of formyl, 40 parts of isopropanol, 12 parts of ammonia, 18 parts of deionized water.
The preparation method of described water soluble acrylate resin, comprises the steps:
1) by butyl acrylate 0-10 part, styrene 0-10 part, Isooctyl acrylate monomer 0-10 part, methacrylic acid 0-15 part, third Olefin(e) acid 0-15 part, hydroxyethyl methylacrylate 0-3 part and Hydroxypropyl acrylate 0-3 part mix homogeneously, obtain monomer mixture;
2) benzoyl peroxide is dissolved in methyl methacrylate, obtains mixed solution;
3) by step 2) in the mixed solution that obtains add in the monomer mixture of step 1), stir;
4) the step 3) mixed liquor that isopropanol and mass ratio are 30% is added in reactor, stir and be warming up to 80-85 DEG C;Open Beginning Deca remaining step 3) mixed liquor enters reactor to start to react;
5), after the whole completion of dropwise addition of step 3) mixed liquor, insulation;
6) after, insulation terminates, rise high-temperature to 90-95 DEG C, start to distill isopropanol solvent, and measure and reclaim;
7), when isopropanol distills out 15-35, stop distillation, and be cooled to 70-80 DEG C;
8), after temperature of reaction kettle is to 70-80 DEG C, add ammonia, and stir;Deionized water is added reactor, at a high speed It is uniformly dispersed;Temperature of reaction kettle is down to 50-60 DEG C, discharging is packaged to be water soluble acrylate resin.
In step 4), time for adding is 2-3 hour, and reaction temperature is 80-85 DEG C.
Holding temperature described in step 5) is 80-85 DEG C, and temperature retention time is 2-3 hour.
The amount of the isopropanol distilling out in step 7) is 15-30 part.
Application in preparing aqueous woodware paint for the described water soluble acrylate resin.
The mass fraction of each material of described aqueous woodware paint is as follows: 70 parts of water soluble acrylate resin, 70 parts of water, specially With 20 parts of firming agent.0.2 part of silicone defoamer, 1.0 parts of silicone levelling agent can also be added.
Special curing agent is purchased from Jiangsu Li Wenjia Chemical Co., Ltd., model lwj-75.
Beneficial effect:
The aqueous woodware paint that the water soluble acrylate resin of the present invention is configured, has film good physical performance, high rigidity, height Gloss and the good feature of richness.Simultaneously using safety, save resources and the energy, reduce the advantages of environmental pollution and public hazards.
Specific embodiment
Embodiment 1
Water soluble acrylate resin, is prepared from by the raw material of following mass fraction: methyl methacrylate 30g, acrylic acid Butyl ester 3g, Isooctyl acrylate monomer 2g, methacrylic acid 12g, hydroxyethyl methylacrylate 1g, benzoyl peroxide 1.5g, isopropyl Alcohol 40g, the ammonia 10g of 25% mass concentration, deionized water 25g.
Polymerization technique is as follows:
(1), by the butyl acrylate of formula ratio, Isooctyl acrylate monomer, methacrylic acid, hydroxyethyl methylacrylate mixes Uniformly, standby;
(2), the benzoyl peroxide of formula ratio is all dissolved in methyl methacrylate;
(3), (2) mixed liquor is added in (1), standby after stirring.
(4), (3) mixed liquor of the isopropanol of formula ratio and 14.8g is added reactor, start and stir and be warming up to 82 DEG C, beginning Deca remaining (3) mixed liquor enters reactor to start to react, time for adding 2.5 hours, reaction temperature 82-85 DEG C;
(5), after completion of dropwise addition, it is incubated 2.5 hours;
(6), it is warming up to 95 degree, distill out isopropanol 20g;
(7), it is cooled to 75 DEG C;
(8), the ammonia of formula ratio is added reactor, stir;
(9), the deionized water of formula ratio is added reactor, be uniformly dispersed at a high speed;
(10), temperature of reaction kettle is down to 50-60 DEG C, filtering and discharging is packed.
Embodiment 2
Water soluble acrylate resin, is prepared from by the raw material of following mass fraction: methyl methacrylate 25g, styrene 5, butyl acrylate 5g, acrylic acid 12g, Hydroxypropyl acrylate 1.5g, benzoyl peroxide 3.0g, isopropanol 40g, 25% concentration Ammonia 11g, deionized water 30g.
Polymerization technique is as follows:
(1), by the styrene of formula ratio, butyl acrylate, acrylic acid, Hydroxypropyl acrylate mix homogeneously, standby;
(2), the benzoyl peroxide of formula ratio is all dissolved in methyl methacrylate;
(3), (2) mixed liquor is added in (1), standby after stirring;
(4), (3) mixed liquor of the isopropanol of formula ratio and 15.1g is added reactor, start and stir and be warming up to 82 ℃.Beginning Deca remaining (3) mixed liquor enters reactor to start to react, time for adding 2.0 hours, reaction temperature 82-85 DEG C;
(5), after completion of dropwise addition, it is incubated 3.0 hours;
(6), it is warming up to 95 degree, distill out isopropanol 20g;
(7), it is cooled to 75 DEG C;
(8), the ammonia of formula ratio is added reactor, stir;
(9), the deionized water of formula ratio is added reactor, be uniformly dispersed at a high speed;
(10), temperature of reaction kettle is down to 50-60 DEG C, filtering and discharging is packed.
Embodiment 3
Water soluble acrylate resin, is prepared from by the raw material of following mass fraction: methyl methacrylate 30g, acrylic acid Butyl ester 7g, methacrylic acid 5g, acrylic acid 7g, Hydroxypropyl acrylate 1.5g, benzoyl peroxide 2.5g, isopropanol 40g, 25% The ammonia 12g of concentration, deionized water 30g.
Polymerization technique is as follows:
(1), by the butyl acrylate of formula ratio, methacrylic acid, acrylic acid, Hydroxypropyl acrylate mix homogeneously, standby;
(2), the benzoyl peroxide of formula ratio is all dissolved in methyl methacrylate;
(3), (2) mixed liquor is added in (1), standby after stirring;
(4), (3) mixed liquor of the isopropanol of formula ratio and 15.9g is added reactor, start and stir and be warming up to 82 ℃;Beginning Deca remaining (3) mixed liquor enters reactor to start to react, time for adding 3.0 hours, reaction temperature 82-85 DEG C;
(5), after completion of dropwise addition, it is incubated 2.0 hours;
(6), it is warming up to 95 degree, distill out isopropanol 20g;
(7), it is cooled to 75 DEG C;
(8), the ammonia of formula ratio is added reactor, stir;
(9), the deionized water of formula ratio is added reactor, be uniformly dispersed at a high speed;
(10), temperature of reaction kettle is down to 50-60 DEG C, filtering and discharging is packed.
Embodiment 4
Aqueous woodware paint is prepared using the formula in such as table 1, the product of embodiment 1-3 is tested, result is as follows:
Table 1 aqueous wooden ware paint formula (consumption of each component is mass fraction)
Water soluble acrylic resin of the present invention 70
Water 70
Special curing agent 20
Special curing agent is purchased from Jiangsu Li Wenjia Chemical Co., Ltd., model lwj-75.
By standard " gb/t 23999-2009 indoor decorating water-borne wood coating ", the product of embodiment 1-3 is examined Survey, the results are shown in Table 2.
Table 2 embodiment 1-3 product aqueous woodware paint testing result
Above-mentioned embodiment is only the certain embodiments in the present invention, does not enumerate the reason because of article length, as long as according to this The know-why of invention carries out equivalent modifications or proportioning change in formula given to this invention and technique to examples detailed above, all Belong to the scope of the present invention.

Claims (8)

1. a kind of water soluble acrylate resin is it is characterised in that be prepared from by the raw material of following mass fraction: metering system Sour methyl ester 20-30 part, styrene 0-10 part, butyl acrylate 0-10 part, Isooctyl acrylate monomer 0-10 part, methacrylic acid 0-15 Part, acrylic acid 0-15 part, hydroxyethyl methylacrylate 0-3 part, Hydroxypropyl acrylate 0-3 part, benzoyl peroxide 1-3 part is different Propanol 35-45 part, ammonia 10-15 part, deionized water 15-40 part.
2. a kind of water soluble acrylate resin according to claim 1 is it is characterised in that the mass concentration of described ammonia For 25%.
3. a kind of water soluble acrylate resin according to claim 1 is it is characterised in that former by following mass fraction Material is prepared from: 30 parts of methyl methacrylate, 5 parts of butyl acrylate, 5 parts of methacrylic acid, 5 parts of acrylic acid, acrylic acid hydroxyl 1 part of propyl ester, 2 parts of benzoyl peroxide, 40 parts of isopropanol, 12 parts of ammonia, 18 parts of deionized water.
4. water soluble acrylate resin described in any one in claim 1-3 preparation method it is characterised in that include as Lower step:
1) by butyl acrylate 0-10 part, styrene 0-10 part, Isooctyl acrylate monomer 0-10 part, methacrylic acid 0-15 part, third Olefin(e) acid 0-15 part, hydroxyethyl methylacrylate 0-3 part and Hydroxypropyl acrylate 0-3 part mix homogeneously, obtain monomer mixture;
2) benzoyl peroxide is dissolved in methyl methacrylate, obtains mixed solution;
3) by step 2) in the mixed solution that obtains add in the monomer mixture of step 1), stir;
4) the step 3) mixed liquor that isopropanol and mass ratio are 30% is added in reactor, stir and be warming up to 80-85 DEG C;Open Beginning Deca remaining step 3) mixed liquor enters reactor to start to react;
5), after the whole completion of dropwise addition of step 3) mixed liquor, insulation;
6) after, insulation terminates, rise high-temperature to 90-95 DEG C, start to distill isopropanol solvent, and measure and reclaim;
7), when isopropanol distills out 15-30 part, stop distillation, and be cooled to 70-80 DEG C;
8), after temperature of reaction kettle is to 70-80 DEG C, add ammonia, and stir;Deionized water is added reactor, at a high speed It is uniformly dispersed;Temperature of reaction kettle is down to 50-60 DEG C, discharging is packaged to be water soluble acrylate resin.
5. the preparation method of water soluble acrylate resin according to claim 4 is it is characterised in that Deca in step 4) Time is 2-3 hour, and reaction temperature is 80-85 DEG C.
6. the preparation method of water soluble acrylate resin according to claim 4 is it is characterised in that described in step 5) Holding temperature is 80-85 DEG C, and temperature retention time is 2-3 hour.
7. application in preparing aqueous woodware paint for the water soluble acrylate resin described in claim 1.
8. application according to claim 7 is it is characterised in that the mass fraction of each material of described aqueous woodware paint is as follows: 70 parts of water soluble acrylate resin, 70 parts of water, 20 parts of special curing agent.
CN201610800277.1A 2016-08-31 2016-08-31 Water-soluble acrylate resin and synthesis method thereof Pending CN106349422A (en)

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106832093A (en) * 2017-02-13 2017-06-13 汕头市金森源化工股份有限公司 A kind of water-soluble thermoplastic acrylic resin and preparation method thereof
CN106832107A (en) * 2017-02-13 2017-06-13 汕头市金森源化工股份有限公司 A kind of thermoplasticity ceramic cover ink resin and preparation method thereof
CN106832092A (en) * 2017-02-13 2017-06-13 汕头市金森源化工股份有限公司 A kind of benzene-free ketone-free food-grade thermoplastic resin and preparation method thereof
CN106832079A (en) * 2017-02-13 2017-06-13 汕头市金森源化工股份有限公司 One kind is without benzene thermosetting acrylic resin and preparation method thereof
CN108178811A (en) * 2017-12-29 2018-06-19 安徽科邦树脂科技有限公司 A kind of water soluble acrylate resin
CN108929402A (en) * 2018-09-04 2018-12-04 厦门纬达树脂有限公司 A kind of solution-type acrylic solution slurry production method
CN109054500A (en) * 2018-08-14 2018-12-21 江西安德力高新科技有限公司 A kind of ink resin and preparation method thereof
CN109679017A (en) * 2019-01-04 2019-04-26 湖北双键精细化工有限公司 A kind of single-component water-based acrylic acid dispersion and preparation method thereof
CN111285957A (en) * 2020-03-11 2020-06-16 西北民族大学 Water dispersible hydroxy acrylic resin and preparation method thereof
US20210253763A1 (en) * 2020-02-14 2021-08-19 Isquared Ag Copolymer for use in a digital manufacturing process
CN113801532A (en) * 2021-09-27 2021-12-17 江苏乐离新材料科技有限公司 Polyacrylate organic silicon modified water-soluble equipment protective film solution and preparation method thereof
CN113881304A (en) * 2021-10-14 2022-01-04 江苏乐离新材料科技有限公司 Nano silicon dioxide modified polyacrylate water-soluble equipment protective film solution and preparation method thereof

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CN101177468A (en) * 2007-12-05 2008-05-14 东莞市英科水墨有限公司 Water-soluble crylic acid resin and preparation method thereof
CN104356291A (en) * 2014-10-26 2015-02-18 大足县众科管道设备有限公司 Method for synthesizing aqueous hydroxyl polyacrylate dispersoid
CN104403044A (en) * 2014-11-12 2015-03-11 马鞍山优科化工有限公司 Finishing water-soluble acrylic resin and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN101177468A (en) * 2007-12-05 2008-05-14 东莞市英科水墨有限公司 Water-soluble crylic acid resin and preparation method thereof
CN104356291A (en) * 2014-10-26 2015-02-18 大足县众科管道设备有限公司 Method for synthesizing aqueous hydroxyl polyacrylate dispersoid
CN104403044A (en) * 2014-11-12 2015-03-11 马鞍山优科化工有限公司 Finishing water-soluble acrylic resin and preparation method thereof

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106832093A (en) * 2017-02-13 2017-06-13 汕头市金森源化工股份有限公司 A kind of water-soluble thermoplastic acrylic resin and preparation method thereof
CN106832107A (en) * 2017-02-13 2017-06-13 汕头市金森源化工股份有限公司 A kind of thermoplasticity ceramic cover ink resin and preparation method thereof
CN106832092A (en) * 2017-02-13 2017-06-13 汕头市金森源化工股份有限公司 A kind of benzene-free ketone-free food-grade thermoplastic resin and preparation method thereof
CN106832079A (en) * 2017-02-13 2017-06-13 汕头市金森源化工股份有限公司 One kind is without benzene thermosetting acrylic resin and preparation method thereof
CN108178811A (en) * 2017-12-29 2018-06-19 安徽科邦树脂科技有限公司 A kind of water soluble acrylate resin
CN109054500A (en) * 2018-08-14 2018-12-21 江西安德力高新科技有限公司 A kind of ink resin and preparation method thereof
CN108929402A (en) * 2018-09-04 2018-12-04 厦门纬达树脂有限公司 A kind of solution-type acrylic solution slurry production method
CN109679017A (en) * 2019-01-04 2019-04-26 湖北双键精细化工有限公司 A kind of single-component water-based acrylic acid dispersion and preparation method thereof
CN109679017B (en) * 2019-01-04 2021-05-14 湖北双键精细化工有限公司 Single-component aqueous acrylic acid dispersion and preparation method thereof
US20210253763A1 (en) * 2020-02-14 2021-08-19 Isquared Ag Copolymer for use in a digital manufacturing process
US11767387B2 (en) * 2020-02-14 2023-09-26 Isquared Ag Copolymer for use in a digital manufacturing process
CN111285957A (en) * 2020-03-11 2020-06-16 西北民族大学 Water dispersible hydroxy acrylic resin and preparation method thereof
CN113801532A (en) * 2021-09-27 2021-12-17 江苏乐离新材料科技有限公司 Polyacrylate organic silicon modified water-soluble equipment protective film solution and preparation method thereof
CN113881304A (en) * 2021-10-14 2022-01-04 江苏乐离新材料科技有限公司 Nano silicon dioxide modified polyacrylate water-soluble equipment protective film solution and preparation method thereof

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Application publication date: 20170125