CN107880258A - Low viscosity modified polyester acrylate ester and preparation method thereof - Google Patents
Low viscosity modified polyester acrylate ester and preparation method thereof Download PDFInfo
- Publication number
- CN107880258A CN107880258A CN201710970222.XA CN201710970222A CN107880258A CN 107880258 A CN107880258 A CN 107880258A CN 201710970222 A CN201710970222 A CN 201710970222A CN 107880258 A CN107880258 A CN 107880258A
- Authority
- CN
- China
- Prior art keywords
- preparation
- reactor
- acid
- solvent
- polyester acrylate
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention proposes a kind of preparation method of low viscosity modified polyester acrylate ester; including 1) polyacid, polyalcohol, catalyst, antioxidant are dissolved in the solvent in reactor; it is passed through nitrogen simultaneously to be protected, is warming up to 135~145 DEG C, insulation treats acid number close to 5mgKOH/g；2) reactor is cooled to 75~85 DEG C, adds acrylic acid and polymerization inhibitor thereto, then heats to 120~125 DEG C, continues reaction to acid number in reactor and is less than 10mgKOH/g；3) reactor is vacuumized, removes reflux solvent, 75~85 DEG C of dischargings are cooled to after solvent is cleared, that is, polyester acrylate is made.The invention also provides low viscosity modified polyester acrylate ester product made from above-mentioned preparation method.The viscosity of the polyester acrylic fat of the present invention is low, can both be used as oligomer, can also be used as activity diluting monomer, and polyester acrylic fat smell is light in addition, and stimulation is small, therefore the injury to body is smaller.
Description
Technical field
The invention belongs to paint field, in particular to a kind of low viscosity modified polyester acrylate ester and preparation method thereof.
Background technology
PEPA can be combined into not due to its extensive basic raw material by different polyalcohol and polyacid
With the PEPA of performance, all it is widely used in coating industry-by-industry.Conventional PEPA is not general single
Film is alone become, polyester-amine baking varnish, PAUR paint, unsaturated polyester varnish need to be configured to, gained coating film gloss is high, plentiful
Spend, weatherability is strong, wetability is good, while its to be formulated design theory ripe.If the performance of PEPA is incorporated into ultraviolet
Curing field, it will be expanded significantly and uses field.
UV-cured resin develops to the direction of low-viscosity at present, and epoxy acrylate and urethane acrylate one
As viscosity it is larger, need to add more reactive diluent could obtain relatively low viscosity, can so reduce the performance of coating, together
When some diluents have stronger excitant and volatility, environmental and human health impacts are all had a certain impact.
The content of the invention
It is an object of the invention to propose a kind of low viscosity modified polyester acrylate ester and preparation method thereof, modified polyester
Acrylate has the characteristics of viscosity is low, and synthesis cost is low, and has a wide range of application, and smell is light, small to body harm.
In order to solve the above technical problems, the present invention is achieved using following technical scheme：
A kind of preparation method of low viscosity modified polyester acrylate ester, comprises the following steps：
1) polyacid, polyalcohol, catalyst, antioxidant are dissolved in the solvent in reactor, while are passed through nitrogen progress
Protection, 135~145 DEG C are warming up to, insulation treats acid number close to 5mgKOH/g；
2) reactor is cooled to 75~85 DEG C, adds acrylic acid and polymerization inhibitor thereto, then heats to 120~125 DEG C,
Continue reaction to acid number in reactor and be less than 10mgKOH/g；
3) start to vacuumize reactor, remove reflux solvent, 75~85 DEG C of dischargings are cooled to after solvent is cleared, that is, are made
Obtain polyester acrylate.
Preferably, the mass fraction of each component is as follows in step 1)：
40~60 parts of polyacid, 30~50 parts of polyalcohol, 0.3~0.8 part of catalyst, 0.08~0.12 part of antioxidant, third
8~15 parts of olefin(e) acid, 0.3~0.8 part of polymerization inhibitor.
Preferably, the polyacid is one kind in adipic acid, suberic acid, THPA, hexahydro M-phthalic acid
It is or a variety of.
Preferably, the polyalcohol is ethylene glycol, neopentyl glycol, 1,6 hexylene glycols, one kind in pentaerythrite or more
Kind.
Preferably, the catalyst is p-methyl benzenesulfonic acid.
Preferably, the antioxidant is at least one of hypophosphorous acid and hydroquinones.
Preferably, the solvent is toluene or dimethylbenzene.
Preferably, the polymerization inhibitor is at least one of MEHQ and 2,6 di-tert-butylphenols.
The invention also provides low viscosity modified polyester acrylate ester made from above-mentioned preparation method.
The present invention have the advantage that compared with prior art for：The viscosity of the polyester acrylic fat of the present invention is low, is
Viscosity 200-500cps, oligomer can be both used as, can also be used as activity diluting monomer, in addition polyester acrylic fat gas
Lightly seasoned, stimulation is small, and therefore, the injury to body is smaller.The cost of raw material entirely used is relatively low, and product has well flexible
Property, pigment wettability the advantages that, therefore be widely used as Photocurable adhesive, the neck such as light-curable ink and other photocureable coating
Domain.
Embodiment
The present invention is got information about to allow those skilled in the art to become apparent from, the present invention will be made below further
Explanation.
Embodiment 1
The preparation method for the low viscosity modified polyester acrylate ester that the present embodiment is related to, comprises the following steps：
1) solvent being dissolved in 40 parts of polyacids, 30 parts of polyalcohols, 0.3 part of catalyst, 0.08 part of antioxidant in reactor
In, while be passed through nitrogen and protected, 135~145 DEG C are warming up to, insulation treats acid number close to 5mgKOH/g；
2) reactor is cooled to 75~85 DEG C, adds 8 parts of acrylic acid and 0.3 part of polymerization inhibitor thereto, then heats to 120
~125 DEG C, continue reaction to acid number in reactor and be less than 10mgKOH/g；
3) start to vacuumize reactor, remove reflux solvent, 75~85 DEG C of dischargings are cooled to after solvent is cleared, that is, are made
Obtain polyester acrylate.
Embodiment 2
The preparation method for the low viscosity modified polyester acrylate ester that the present embodiment is related to, comprises the following steps：
1) solvent being dissolved in 50 parts of polyacids, 40 parts of polyalcohols, 0.5 part of catalyst, 0.1 part of antioxidant in reactor
In, while be passed through nitrogen and protected, 135~145 DEG C are warming up to, insulation treats acid number close to 5mgKOH/g；
2) reactor is cooled to 75~85 DEG C, adds 10 parts of acrylic acid and 0.5 part of polymerization inhibitor thereto, then heats to
120~125 DEG C, continue reaction to acid number in reactor and be less than 10mgKOH/g；
3) start to vacuumize reactor, remove reflux solvent, 75~85 DEG C of dischargings are cooled to after solvent is cleared, that is, are made
Obtain polyester acrylate.
Embodiment 3
The preparation method for the low viscosity modified polyester acrylate ester that the present embodiment is related to, comprises the following steps：
1) solvent being dissolved in 60 parts of polyacids, 50 parts of polyalcohols, 0.8 part of catalyst, 0.12 part of antioxidant in reactor
In, while be passed through nitrogen and protected, 135~145 DEG C are warming up to, insulation treats acid number close to 5mgKOH/g；
2) reactor is cooled to 75~85 DEG C, adds 15 parts of acrylic acid and 0.8 part of polymerization inhibitor thereto, then heats to
120~125 DEG C, continue reaction to acid number in reactor and be less than 10mgKOH/g；
3) start to vacuumize reactor, remove reflux solvent, 75~85 DEG C of dischargings are cooled to after solvent is cleared, that is, are made
Obtain polyester acrylate.
In embodiment 1~3, the polyacid is one in adipic acid, suberic acid, THPA, hexahydro M-phthalic acid
Kind is a variety of；The polyalcohol is the one or more in ethylene glycol, neopentyl glycol, 1,6 hexylene glycols, pentaerythrite；It is described to urge
Agent is p-methyl benzenesulfonic acid；The antioxidant is at least one of hypophosphorous acid and hydroquinones；The solvent be toluene or
Dimethylbenzene；The polymerization inhibitor is at least one of MEHQ and 2,6 di-tert-butylphenols.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
God any modification, equivalent substitution and improvements made etc., should be included in the scope of the protection with principle.
Claims (9)
1. a kind of preparation method of low viscosity modified polyester acrylate ester, it is characterised in that comprise the following steps：
1) polyacid, polyalcohol, catalyst, antioxidant are dissolved in the solvent in reactor, while are passed through nitrogen and are protected,
135~145 DEG C are warming up to, insulation treats acid number close to 5mgKOH/g；
2) reactor is cooled to 75~85 DEG C, adds acrylic acid and polymerization inhibitor thereto, then heats to 120~125 DEG C, reaction
Continue reaction to acid number in kettle and be less than 10mgKOH/g；
3) start to vacuumize reactor, remove reflux solvent, 75~85 DEG C of dischargings are cooled to after solvent is cleared, that is, be made poly-
Ester acrylate.
2. preparation method according to claim 1, it is characterised in that, the mass fraction of each component is as follows in step 1)：
40~60 parts of polyacid, 30~50 parts of polyalcohol, 0.3~0.8 part of catalyst, 0.08~0.12 part of antioxidant, acrylic acid 8
~15 parts, 0.3~0.8 part of polymerization inhibitor.
3. preparation method according to claim 1 or 2, it is characterised in that the polyacid is adipic acid, suberic acid, four
One or more in hydrogen phthalic anhydride, hexahydro M-phthalic acid.
4. preparation method according to claim 1 or 2, it is characterised in that the polyalcohol be ethylene glycol, neopentyl glycol,
One or more in 1,6 hexylene glycols, pentaerythrite.
5. preparation method according to claim 1 or 2, it is characterised in that the catalyst is p-methyl benzenesulfonic acid.
6. preparation method according to claim 1 or 2, it is characterised in that the antioxidant is hypophosphorous acid and hydroquinones
At least one of.
7. preparation method according to claim 1 or 2, it is characterised in that the solvent is toluene or dimethylbenzene.
8. preparation method according to claim 1 or 2, it is characterised in that the polymerization inhibitor is MEHQ and 2,6
At least one of di-tert-butylphenol.
9. low viscosity modified polyester acrylate ester made from preparation method according to claim 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710970222.XA CN107880258A (en) | 2017-10-16 | 2017-10-16 | Low viscosity modified polyester acrylate ester and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710970222.XA CN107880258A (en) | 2017-10-16 | 2017-10-16 | Low viscosity modified polyester acrylate ester and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107880258A true CN107880258A (en) | 2018-04-06 |
Family
ID=61781699
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710970222.XA Pending CN107880258A (en) | 2017-10-16 | 2017-10-16 | Low viscosity modified polyester acrylate ester and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107880258A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109627726A (en) * | 2018-11-22 | 2019-04-16 | 株洲时代电气绝缘有限责任公司 | A kind of pure resin type polyester epoxy environmental protection impregnating resin and preparation method thereof |
| CN110105851A (en) * | 2019-04-28 | 2019-08-09 | 英德市雅家涂料有限公司 | A kind of quick-setting UV polyester acrylate of low viscosity and its preparation process |
| CN111978530A (en) * | 2020-08-31 | 2020-11-24 | 江苏三木化工股份有限公司 | Low-viscosity high-cost-performance polyester acrylate and preparation method thereof |
| CN113546763A (en) * | 2021-07-20 | 2021-10-26 | 湖南聚仁化工新材料科技有限公司 | Mineral flotation foaming agent and preparation method and application thereof |
| CN115304479A (en) * | 2022-07-22 | 2022-11-08 | 嘉宝莉化工集团股份有限公司 | Preparation method and application of washing-free solvent-free modified UV monomer |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735441A (en) * | 2009-12-08 | 2010-06-16 | 自贡拓力化工有限公司 | Method for preparing ultraviolet curing polyester acrylic ester prepolymer |
| CN105061739A (en) * | 2015-09-08 | 2015-11-18 | 常州华科聚合物股份有限公司 | Paint resin for cans/tins and preparation method thereof, and paint composition for cans/tins |
| CN105254862A (en) * | 2015-10-20 | 2016-01-20 | 三棵树涂料股份有限公司 | Rapidly cured UV (ultraviolet) polyester acrylate with high scratch resistance and preparation method of UV polyester acrylate |
-
2017
- 2017-10-16 CN CN201710970222.XA patent/CN107880258A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735441A (en) * | 2009-12-08 | 2010-06-16 | 自贡拓力化工有限公司 | Method for preparing ultraviolet curing polyester acrylic ester prepolymer |
| CN105061739A (en) * | 2015-09-08 | 2015-11-18 | 常州华科聚合物股份有限公司 | Paint resin for cans/tins and preparation method thereof, and paint composition for cans/tins |
| CN105254862A (en) * | 2015-10-20 | 2016-01-20 | 三棵树涂料股份有限公司 | Rapidly cured UV (ultraviolet) polyester acrylate with high scratch resistance and preparation method of UV polyester acrylate |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109627726A (en) * | 2018-11-22 | 2019-04-16 | 株洲时代电气绝缘有限责任公司 | A kind of pure resin type polyester epoxy environmental protection impregnating resin and preparation method thereof |
| CN109627726B (en) * | 2018-11-22 | 2021-07-30 | 株洲时代电气绝缘有限责任公司 | Pure resin type polyester epoxy environment-friendly impregnating resin and preparation method thereof |
| CN110105851A (en) * | 2019-04-28 | 2019-08-09 | 英德市雅家涂料有限公司 | A kind of quick-setting UV polyester acrylate of low viscosity and its preparation process |
| CN110105851B (en) * | 2019-04-28 | 2021-06-04 | 英德市雅家涂料有限公司 | Low-viscosity fast-curing UV polyester acrylate and preparation process thereof |
| CN111978530A (en) * | 2020-08-31 | 2020-11-24 | 江苏三木化工股份有限公司 | Low-viscosity high-cost-performance polyester acrylate and preparation method thereof |
| CN113546763A (en) * | 2021-07-20 | 2021-10-26 | 湖南聚仁化工新材料科技有限公司 | Mineral flotation foaming agent and preparation method and application thereof |
| CN115304479A (en) * | 2022-07-22 | 2022-11-08 | 嘉宝莉化工集团股份有限公司 | Preparation method and application of washing-free solvent-free modified UV monomer |
| CN115304479B (en) * | 2022-07-22 | 2023-08-15 | 嘉宝莉化工集团股份有限公司 | Preparation method and application of water-washing-free solvent-free modified UV monomer |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107880258A (en) | Low viscosity modified polyester acrylate ester and preparation method thereof | |
| US9266292B2 (en) | Epoxy acid thermoset resins and composites that can be hot-fashioned and recycled | |
| EP2411445B1 (en) | Unsaturated polyester resin | |
| TWI618727B (en) | Curable resin compositions | |
| US20140088223A1 (en) | Thermoset/supramolecular hybrid composites and resins that can be hot-formed and recycled | |
| JP6096657B2 (en) | High functional polyester and coating containing the same | |
| CN109476077A (en) | The method and composition to form three-dimension object is manufactured by addition process | |
| JP2022043187A (en) | Latex coating composition having reduced flavor scalping properties | |
| WO2003080745A1 (en) | Uv-curable coating composition and coated articles | |
| EP3172257B1 (en) | Matt powder coatings | |
| Sahoo et al. | Synthesis and characterization of low viscous and highly acrylated epoxidized methyl ester based green adhesives derived from linseed oil | |
| TW201249928A (en) | Non-aqueous dispersions comprising a polyester stabilizer and their use in coatings | |
| KR20220112308A (en) | Radiation curing coating composition | |
| JPWO2018021352A1 (en) | Curing type composition | |
| CN104610890B (en) | Preparation method of modified chlorinated polypropylene adhesive | |
| CN108383989A (en) | A kind of epoxy acrylic resin and its preparation method and application of two degrees of functionality | |
| JP5493424B2 (en) | Active energy ray curable lithographic printing ink and printed matter thereof | |
| EP2935349A1 (en) | Catalytic systems for thermosetting resins which are deformable in the thermoset state | |
| JP2010070743A (en) | Active energy ray curing type lithographic ink and printed matter thereof | |
| JP2010229298A (en) | Active energy ray-curable planographic printing ink and printed matter thereof | |
| JPS63145372A (en) | Actinic radiation curable paint | |
| KR101907532B1 (en) | Unsaturated mixture resin part for putty and method for forming putty layer | |
| WO2013141117A1 (en) | Active energy ray-curable composition, active energy ray-curable coating material using same, and active energy ray-curable printing ink using same | |
| JP2012092234A (en) | Active energy ray-curable lithographic ink and printed matter of the same | |
| KR102333935B1 (en) | Epoxy Resin Manufacturing Method |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180406 |
|
| RJ01 | Rejection of invention patent application after publication |