CN105906792B - A kind of heat-resisting chemically-resistant and color inhibition unsaturated polyester resin and preparation method thereof - Google Patents
A kind of heat-resisting chemically-resistant and color inhibition unsaturated polyester resin and preparation method thereof Download PDFInfo
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- CN105906792B CN105906792B CN201610482500.2A CN201610482500A CN105906792B CN 105906792 B CN105906792 B CN 105906792B CN 201610482500 A CN201610482500 A CN 201610482500A CN 105906792 B CN105906792 B CN 105906792B
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- polyester resin
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- 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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- 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
- C08G63/78—Preparation processes
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- 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
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
- C08G63/86—Germanium, antimony, or compounds thereof
- C08G63/866—Antimony or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/06—Unsaturated polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a kind of heat-resisting chemically-resistant and color inhibition unsaturated polyester resin, it is prepared from the following raw materials in parts by weight：320 370 parts of binary acid, mixes 250 370 parts of alcohol, 20 200 parts of dihydric alcohol, 400 420 parts of solvent, 1.5 2 parts of catalyst, 0.1 0.5 parts of polymerization inhibitor.The resin has high-fire resistance, and preferably, excellent hydrolytic stability, yellowing resistance is good for chemically-resistant, and solidification post-shrinkage ratio is compared with the low feature of equivalent responses reactive resin.In addition, also disclosing the preparation method of the unsaturated polyester resin, this method has the reaction time moderate, and course of reaction is easily-controllable, the advantage that reaction product is easy to get.
Description
Technical field
The present invention relates to technical field of composite materials, and in particular to a kind of heat-resisting chemically-resistant and color inhibition unsaturated polyester (UP) tree
Fat and preparation method thereof.
Background technology
Unsaturated polyester resin heat resistance is generally relatively low, and most of heat distortion temperature is and heat-resist at 60-70 DEG C
Its heat distortion temperature of resin up to 120 DEG C, metaphenylene polyester resin (such as 199#), the bisphenol A-type of such as high reaction activity are anti-
Butene dioic acid ester polyester resin and epoxy novolac vinylite.But non-modified 199# resin solidification shrinkage factors are higher, resistance to
Xanthochromia is poor, and chemically-resistant level is medium, it is impossible to apply in the product required to cure shrinkage and yellowing resistance, and it is applied
Scope is limited.And the production technology of 199# unsaturated polyester resins must use Liang Walk methods, the reaction time is long, production cost
It is high.
The heat-resisting chemical resistance of bisphenol A-type polyester resin is good, but bisphenol-a derivative price is higher, and resin yellowing resistance compared with
Difference.Vinylite has good heat resistance corrosion resistance and cure shrinkage is not high, but its prices of raw materials is high, production technology
Take it is longer, resin be difficult to stabilization, be only applicable to require the product of excellent properties.
The content of the invention
In view of the shortcomings of the prior art, it is an object of the invention to provide a kind of heat-resisting chemically-resistant and color inhibition unsaturation is poly-
Ester resin.
It is moderate with the reaction time it is a further object of the present invention to provide the preparation method of the unsaturated polyester resin, instead
Answer process easily-controllable, the advantages of reaction product is easy to get.
To achieve the above object, the technical solution adopted for the present invention to solve the technical problems is：
The heat-resisting chemically-resistant of the present invention and color inhibition unsaturated polyester resin, include the raw material of following parts by weight：
Further, the binary acid is one or more in maleic anhydride, fumaric acid, THPA
Mixture.
Further, described dihydric alcohol is one or more mixtures in propane diols, cyclohexanediol.
Further, the mixed alcohol is7 are pressed respectively:2:1 matter
Amount is than being mixed.
Further, the polymerization inhibitor is one kind or many in quinhydrones, methylnaphthohydroquinone, tert-butyl catechol, 1,4-benzoquinone
The mixture planted.
Preferably, the reaction is carried out under the catalysis of catalyst.The catalyst can use this area Conventional catalytic
Agent, preferably antimony glycol.
The reaction is carried out in a solvent.The solvent is the solvent that can be dissolved corresponding raw material but not participate in reaction,
One or more mixtures in optimization styrene, methyl methacrylate.
The preparation method of unsaturated polyester resin of the present invention, comprises the following steps：
(a) binary acid, mixed alcohol, polyalcohol, catalyst and polymerization inhibitor are added in reactor under normal temperature, in inert gas
195-200 DEG C of insulation is progressively warming up under protection from room temperature, takes material in reactor to carry out acid value measuring, when acid number exists
During below 50mgKOH/g, start to vacuumize, until acid number is in below 32mgKOH/g, Cone ＆ Plate viscosity 4500-4800mPa.s/120
DEG C, start cooling.
(b) add polymerization inhibitor and solvent carries out latting drown, then filter, produce unsaturated polyester resin of the present invention.
A kind of heat-resisting chemically-resistant and color inhibition unsaturated polyester resin that the present invention is provided and preparation method thereof, with following
Beneficial effect：
(1) in mixed alcohol and dihydric alcohol substantial amounts of saturation ring structure and symmetrical structure improve resin it is heat-resisting,
While chemical resistance, certain pliability is made it have, cure shrinkage is low compared with equivalent responses reactive resin, and color inhibition
Property is good；
(2) the mixed alcohol steady sources and moderate cost used in raw material, easily with binary acid and anhydride reaction, one-step method
Prepare unsaturated polyester resin of the present invention.
Embodiment
The present invention is further described below by the mode of specific embodiment, but the scope of the present invention does not limit to
In these embodiments.It is all to be based on above-mentioned technological thought, the modification made using ordinary skill knowledge and customary means, replace
Change, change and belong to the scope of protection of present invention.
Alcohol is mixed used in following examples isIn mass ratio 7:2:1
The mixture mixed.
The unsaturated polyester resin A of the present invention of embodiment 1 preparation
(a) 20 DEG C of maleic anhydrides by 235g, 91.3g THPA, 35.5g propane diols, 250g mixed alcohol,
168.9g cyclohexanediols, 0.03g methylnaphthohydroquinones and 2.0g antimony glycols are added in reactor, from room under inert gas shielding
Temperature is warming up to 195-200 DEG C of insulation, takes material in reactor to carry out acid value measuring, when acid number is in below 50mgKOH/g, starts
Vacuumize, until acid number is in below 32mgKOH/g, 4500-4800mPa.s/120 DEG C of Cone ＆ Plate viscosity starts cooling；
(b) 0.08g quinhydrones, 380g styrene and 40g methyl methacrylates are added and carries out latting drown, then filtered, is made
Heat-resisting chemically-resistant and color inhibition unsaturated polyester resin of the present invention.
The unsaturated polyester resin B of the present invention of embodiment 2 preparation
(1) 30 DEG C by 278.6g fumaric acid, 91.3g THPA, 22g propane diols, 368.5g mixed alcohol,
70.6g cyclohexanediols, 0.03g methylnaphthohydroquinones, 2.0g antimony glycols are added in reactor, from room temperature under inert gas shielding
195-200 DEG C of insulation is warming up to, takes material in reactor to carry out acid value measuring, when acid number is in below 50mgKOH/g, starts to take out
Vacuum, until below acid number 32mgKOH/g, 4500-4800mPa.s/120 DEG C of Cone ＆ Plate viscosity, start cooling；
(2) 0.08g quinhydrones, 420g styrene are added and carries out latting drown, then filtered.
The unsaturated polyester resin C of the present invention of embodiment 3 preparation
(1) 25 DEG C by 135g maleic anhydrides, 118.7g fumaric acid, 91.3g THPA, 22g propane diols,
331g mixes alcohol, 0.3g quinhydrones, and 1.5g antimony glycols are added in reactor, from room temperature to 195- under inert gas shielding
200 DEG C of insulations, take material in reactor to carry out acid value measuring, when acid number is in below 50mgKOH/g, start to vacuumize, until
Acid number starts cooling in below 32mgKOH/g, 4500-4800mPa.s/120 DEG C of Cone ＆ Plate viscosity.
(2) 0.03g quinhydrones, 0.15g tert-butyl catechols, 0.03 1,4-benzoquinone and 400g styrene are added and carry out latting drown,
Then filter.
The unsaturated polyester resin generated time of the present invention of embodiment 4 and performance test
Using《GB/T7193-2008 unsaturated polyester resin test methods》To embodiment 1-3 acid number, solids content,
Viscosity, gel time (25 DEG C), 80 DEG C of heat endurances are tested.Embodiment 1 and the pour mass of embodiment 2 according to《GB/T2567-
2008》Carry out normal temperature cure, embodiment 3 according to《GB/T2567-2008》Carry out middle (80 DEG C) solidifications of temperature.The Pasteur of pour mass is hard
Degree test according to《GB/T/3854-2005》, heat distortion temperature test according to《GB/T1634-2004》, chemical resistance test according to
《GB/T3857-2005》, shrinkage factor test according to《GB/T24148.9-2014》.Yellowing resistance test according to《GB23987-
2009》.Other performance indications of pour mass according to《GB/T2567-2008》Tested.The resins synthesis time is by reflecting
Water is calculated to cooling.Testing result is as shown in the table：
The generated time and index of the unsaturated polyester resin of table 1
Conclusion：Heat-resisting chemically-resistant and color inhibition unsaturated polyester resin prepared by the present invention, it is moderate with the reaction time, instead
Answer the characteristics of process is easily-controllable.
The performance indications for the pour mass that unsaturated polyester resin described in table 2 makes
| Embodiment 1 | Embodiment 2 | Embodiment 3 | 199# | |
| Hardness Barcol HBa | 45 | 43 | 43 | 45 |
| Tensile strength MPa | 55 | 58 | 55 | 55 |
| Fracture elongation % | 2.5 | 2.5 | 2.5 | 2 |
| Bending strength MPa | 90 | 90 | 90 | 90 |
| Heat distortion temperature DEG C | 120 | 130 | 125 | 125 |
| Cubical contraction | 8.0 | 8.0 | 8.0 | 8.6 |
Conclusion：Heat-resisting chemically-resistant and color inhibition unsaturated polyester resin prepared by the present invention, with high-fire resistance, fracture is prolonged
Stretch rate slightly higher, the characteristics of more equal reactive resin of cubical contraction is low.
The chemical resistance for the pour mass that unsaturated polyester resin described in table 3 makes
Conclusion：Heat-resisting chemically-resistant and color inhibition unsaturated polyester resin prepared by the present invention, with (metaphenylene gathers with 199#
Ester resin) suitable or slightly good chemical resistance.
Unsaturated polyester resin yellowing resistance described in table 4 is tested
| Embodiment 1 | Embodiment 2 | Embodiment 3 | 199# | |
| Color inhibition △ E | 4.5 | 5.0 | 5.2 | 11.5 |
Conclusion：Heat-resisting chemically-resistant and color inhibition unsaturated polyester resin prepared by the present invention, with good yellowing resistance.
Claims (7)
1. a kind of heat-resisting chemically-resistant and color inhibition unsaturated polyester resin, include the raw material of following parts by weight：
The mixed alcohol isDifference in mass ratio 7:2:1 is mixed.
2. unsaturated polyester resin according to claim 1, it is characterised in that the binary acid be maleic anhydride,
One or more mixtures in fumaric acid, THPA.
3. unsaturated polyester resin according to claim 1, it is characterised in that described dihydric alcohol is propane diols, hexamethylene
One or more mixtures in glycol.
4. unsaturated polyester resin according to claim 1, it is characterised in that the polymerization inhibitor be quinhydrones, methylnaphthohydroquinone,
One or more mixtures in tert-butyl catechol, 1,4-benzoquinone.
5. unsaturated polyester resin according to claim 1, it is characterised in that the catalyst is antimony glycol.
6. unsaturated polyester resin according to claim 1, it is characterised in that the solvent is styrene, metering system
One or more mixtures in sour methyl esters.
7. a kind of preparation method of unsaturated polyester resin as described in claim any one of 1-6, comprises the following steps：
(a) binary acid, mixed alcohol, polyalcohol, catalyst and polymerization inhibitor are added in reactor at 20~30 DEG C, in inert gas
195-200 DEG C of insulation is progressively warming up under protection from room temperature, takes material in reactor to carry out acid value measuring, when acid number exists
During below 50mgKOH/g, start to vacuumize, until acid number is in below 32mgKOH/g, Cone ＆ Plate viscosity 4500-4800mPa.s/120
DEG C, start cooling；
(b) add polymerization inhibitor and solvent carries out latting drown, then filter, produce unsaturated polyester resin of the present invention.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610482500.2A CN105906792B (en) | 2016-06-25 | 2016-06-25 | A kind of heat-resisting chemically-resistant and color inhibition unsaturated polyester resin and preparation method thereof |
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| CN201610482500.2A CN105906792B (en) | 2016-06-25 | 2016-06-25 | A kind of heat-resisting chemically-resistant and color inhibition unsaturated polyester resin and preparation method thereof |
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| CN108503757B (en) * | 2018-02-12 | 2020-07-24 | 浙江博菲电气股份有限公司 | Low-viscosity unsaturated polyester resin for VPI (vacuum pressure impregnation) process and application thereof |
| CN109824829A (en) * | 2019-02-14 | 2019-05-31 | 常州天马集团有限公司（原建材二五三厂） | Sheet molding compound high-intensity and high-tenacity unsaturated polyester resin and preparation method thereof |
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| JPS6330522A (en) * | 1986-07-23 | 1988-02-09 | Showa Highpolymer Co Ltd | Production of unsaturated polyester resin of excellent air dryability |
| CN102060985B (en) * | 2010-12-17 | 2013-04-17 | 常州华科树脂有限公司 | Unsaturated polyester resin for sheet or bulk molding compound and preparation method thereof |
| CN102174177A (en) * | 2011-03-07 | 2011-09-07 | 上海新天和树脂有限公司 | Unsaturated polyester resin for high-yellowing-resistant fiber-reinforced lighting panel and preparation method thereof |
| CN102174176B (en) * | 2011-03-11 | 2012-10-24 | 安徽神剑新材料股份有限公司 | Preparation method of thermosetting type pure polyester resin capable of resisting high-temperature yellowing |
| CN105482087B (en) * | 2015-12-28 | 2018-06-15 | 肇庆福田化学工业有限公司 | A kind of color inhibition unsaturated polyester resin and its synthetic method |
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