CN105906792A - Heat, chemical and yellowing resistant unsaturated polyester resin (UPR) and preparation method thereof - Google Patents
Heat, chemical and yellowing resistant unsaturated polyester resin (UPR) and preparation method thereof Download PDFInfo
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- CN105906792A CN105906792A CN201610482500.2A CN201610482500A CN105906792A CN 105906792 A CN105906792 A CN 105906792A CN 201610482500 A CN201610482500 A CN 201610482500A CN 105906792 A CN105906792 A CN 105906792A
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- polyester resin
- unsaturated polyester
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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
-
- 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
-
- 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
-
- 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 heat, chemical and yellowing resistant unsaturated polyester resin (UPR). The UPR is prepared from the following raw materials in parts by weight: 320-370 parts of dibasic acid, 250-370 parts of mixed alcohol, 20-200 parts of diol, 400-420 parts of solvent, 1.5-2 parts of catalyst and 0.1-0.5 part of polymerization inhibitor. The resin has the characteristics of high heat resistance, better chemical resistance, excellent hydrolytic stability, good yellowing resistance, lower shrinkage than the resin with equal reaction activity after curing, and the like. Besides, the invention also discloses a preparation method of the UPR. The method has the advantages of moderate reaction time, easiness in control of the reaction process and easiness in obtainment of the reaction product.
Description
Technical field
The present invention relates to technical field of composite materials, be specifically related 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 thermostability is the most relatively low, and most of heat distortion temperature is at 60-70 DEG C, and heat-resist
Its heat distortion temperature of resin up to 120 DEG C, the metaphenylene polyester resin (such as 199#) of such as high reaction activity, bisphenol A-type are anti-
Butene dioic acid ester polyester resin and epoxy novolac vinylite.But the 199# resin cure shrinkage of non-modified is higher, resistance to
Xanthochromia is poor, and chemically-resistant level is medium, it is impossible to apply at the product requiring cure shrinkage and yellowing resistance, its application
Scope is limited.And the production technology of 199# unsaturated polyester resin must use two methods, the response time is long, production cost
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 is relatively
Difference.Vinylite has good thermostability corrosion resistance and cure shrinkage the highest, but its prices of raw materials are high, production technology
Taking longer, resin is difficult to stable, is only applicable to the product of requirement excellent properties.
Summary of the invention
For the deficiencies in the prior art, it is an object of the invention to provide a kind of heat-resisting chemically-resistant and color inhibition unsaturated polyester
Ester resin.
It is a further object of the present invention to provide the preparation method of this unsaturated polyester resin, there is the response time moderate, instead
Answering process easily-controllable, product such as is easy to get at the advantage.
For achieving 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, comprise the raw material of following weight portion:
Further, one or more during described binary acid is maleic anhydride, fumaric acid, THPA
Mixture.
Further, described dihydroxylic alcohols is the mixture of one or more in propylene glycol, cyclohexanediol.
Further, described mixed alcohol isPress the matter of 7:2:1 respectively
Amount ratio mixes.
Further, the one or many during described polymerization inhibitor is hydroquinone, methylnaphthohydroquinone, tert-butyl catechol, 1,4-benzoquinone
The mixture planted.
Preferably, described reaction is carried out under the catalysis of catalyst.Described catalyst can use this area Conventional catalytic
Agent, preferably antimony glycol.
Described reaction is carried out in a solvent.Described solvent is to dissolve corresponding raw material but cannot participate in the solvent of reaction,
The mixture of one or more in optimization styrene, methyl methacrylate.
The preparation method of unsaturated polyester resin of the present invention, comprises the steps:
Under (a) room temperature, binary acid, mixed alcohol, polyhydric alcohol, catalyst and polymerization inhibitor are joined in reactor, at noble gas
Progressively it is warming up to 195-200 DEG C of insulation under protection from room temperature, takes material in reactor and carry out acid value measuring, when acid number exists
During below 50mgKOH/g, start evacuation, until acid number is at below 32mgKOH/g, Cone & Plate viscosity 4500-4800mPa.s/120
DEG C, start cooling.
B () adds polymerization inhibitor and solvent carries out latting drown, then filters, obtains unsaturated polyester resin of the present invention.
The heat-resisting chemically-resistant of one of present invention offer and color inhibition unsaturated polyester resin and preparation method thereof, have following
Beneficial effect:
(1) in mixed alcohol and dihydroxylic alcohols substantial amounts of saturated rings structure and symmetrical structure improve resin heat-resisting,
While chemical resistance so that it is have certain pliability, cure shrinkage is low compared with equivalent responses reactive resin, and color inhibition
Property is good；
(2) the mixed alcohol steady sources used in raw material and moderate cost, easy and binary acid and anhydride reaction, one-step method
Prepare unsaturated polyester resin of the present invention.
Detailed description of the invention
Below by the mode of specific embodiment, the present invention is further described, but scope does not limit to
In these embodiments.All based on above-mentioned technological thought, utilize amendment that ordinary skill knowledge and customary means made, replace
Change, change and belong to the scope of protection of present invention.
Used by following example, mixed alcohol is7:2:1 in mass ratio
Carry out the mixture mixed.
The preparation of embodiment 1 unsaturated polyester resin of the present invention A
(a) 20 DEG C by the maleic anhydride of 235g, the THPA of 91.3g, 35.5g propylene glycol, the mixed alcohol of 250g,
168.9g cyclohexanediol, 0.03g methylnaphthohydroquinone and 2.0g antimony glycol join in reactor, from room under inert gas shielding
Temperature is warming up to 195-200 DEG C of insulation, takes material in reactor and carries out acid value measuring, when acid number is at below 50mgKOH/g, starts
Evacuation, until acid number is at below 32mgKOH/g, Cone & Plate viscosity 4500-4800mPa.s/120 DEG C, starts cooling；
B () adds 0.08g hydroquinone, 380g styrene and 40g methyl methacrylate and carries out latting drown, then filter, and prepares
Heat-resisting chemically-resistant of the present invention and color inhibition unsaturated polyester resin.
The preparation of embodiment 2 unsaturated polyester resin of the present invention B
(1) 30 DEG C by the fumaric acid of 278.6g, the THPA of 91.3g, 22g propylene glycol, the mixed alcohol of 368.5g,
70.6g cyclohexanediol, 0.03g methylnaphthohydroquinone, 2.0g antimony glycol joins in reactor, from room temperature under inert gas shielding
It is warming up to 195-200 DEG C of insulation, takes material in reactor and carry out acid value measuring, when acid number is at below 50mgKOH/g, start to take out
Vacuum, until below acid number 32mgKOH/g, Cone & Plate viscosity 4500-4800mPa.s/120 DEG C, starts cooling；
(2) add 0.08g hydroquinone, 420g styrene carries out latting drown, then filters.
The preparation of embodiment 3 unsaturated polyester resin of the present invention C
(1) 25 DEG C by 135g maleic anhydride, 118.7g fumaric acid, the THPA of 91.3g, 22g propylene glycol,
331g mixes alcohol, 0.3g hydroquinone, and 1.5g antimony glycol joins in reactor, from room temperature to 195-under inert gas shielding
200 DEG C of insulations, take material in reactor and carry out acid value measuring, when acid number is at below 50mgKOH/g, start evacuation, until
Acid number, at below 32mgKOH/g, Cone & Plate viscosity 4500-4800mPa.s/120 DEG C, starts cooling.
(2) add 0.03g hydroquinone, 0.15g tert-butyl catechol, 0.03 1,4-benzoquinone and 400g styrene and carry out latting drown,
Then filter.
Embodiment 4 unsaturated polyester resin of the present invention generated time and performance test
Use " GB/T7193-2008 unsaturated polyester resin test method " to the acid number of embodiment 1-3, solids content,
Viscosity, gel time (25 DEG C), 80 DEG C of heat stability are tested.Embodiment 1 and embodiment 2 pour mass are according to " GB/T2567-
2008 " carrying out normal temperature cure, embodiment 3 carries out middle temperature (80 DEG C) solidification according to " GB/T2567-2008 ".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 is tested according to " GB/T24148.9-2014 ".Yellowing resistance is tested according to " GB23987-
2009》.Other performance indications of pour mass are all tested according to " GB/T2567-2008 ".The resins synthesis time is by reflecting
Water calculates to cooling.Testing result is as shown in the table:
The generated time of table 1 unsaturated polyester resin and index
Conclusion: heat-resisting chemically-resistant prepared by the present invention and color inhibition unsaturated polyester resin, has the response time moderate, instead
Answer the feature that process is easily-controllable.
The performance indications of 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 |
| Hot 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 prepared by the present invention and color inhibition unsaturated polyester resin, has high-fire resistance, and fracture is prolonged
Rate of stretching is slightly higher, the feature that the more equal reactive resin of cubical contraction is low.
The chemical resistance of the pour mass that unsaturated polyester resin described in table 3 makes
Conclusion: heat-resisting chemically-resistant prepared by the present invention and color inhibition unsaturated polyester resin, has with 199# that (metaphenylene gathers
Ester resin) quite or the best chemical resistance.
Unsaturated polyester resin yellowing resistance test described in table 4
| Embodiment 1 | Embodiment 2 | Embodiment 3 | 199# | |
| Color inhibition △ E | 4.5 | 5.0 | 5.2 | 11.5 |
Conclusion: heat-resisting chemically-resistant prepared by the present invention and color inhibition unsaturated polyester resin, has good yellowing resistance.
Claims (8)
1. heat-resisting chemically-resistant and a color inhibition unsaturated polyester resin, comprises the raw material of following weight portion:
Unsaturated polyester resin the most according to claim 1, it is characterised in that described binary acid be maleic anhydride,
The mixture of one or more in fumaric acid, THPA.
Unsaturated polyester resin the most according to claim 1, it is characterised in that described dihydroxylic alcohols is propylene glycol, hexamethylene
The mixture of one or more in glycol.
Unsaturated polyester resin the most according to claim 1, it is characterised in that described mixed alcohol is 7:2:1 the most in mass ratio mixes.
Unsaturated polyester resin the most according to claim 1, it is characterised in that described polymerization inhibitor be hydroquinone, methylnaphthohydroquinone,
The mixture of one or more in tert-butyl catechol, 1,4-benzoquinone.
Unsaturated polyester resin the most according to claim 1, it is characterised in that described catalyst is antimony glycol.
Unsaturated polyester resin the most according to claim 1, it is characterised in that described solvent is styrene, metering system
The mixture of one or more in acid methyl ester.
8. a preparation method for the unsaturated polyester resin as described in any one of claim 1-7, comprises the steps:
At (a) 20～30 DEG C, binary acid, mixed alcohol, polyhydric alcohol, catalyst and polymerization inhibitor are joined in reactor, at noble gas
Progressively it is warming up to 195-200 DEG C of insulation under protection from room temperature, takes material in reactor and carry out acid value measuring, when acid number exists
During below 50mgKOH/g, start evacuation, until acid number is at below 32mgKOH/g, Cone & Plate viscosity 4500-4800mPa.s/120
DEG C, start cooling.
B () adds polymerization inhibitor and solvent carries out latting drown, then filters, obtains unsaturated polyester resin of the present invention.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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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| CN105906792A true CN105906792A (en) | 2016-08-31 |
| CN105906792B CN105906792B (en) | 2017-10-27 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108503757A (en) * | 2018-02-12 | 2018-09-07 | 嘉兴市新大陆机电有限公司 | A kind of VPI impregnation technologies low viscosity unsaturated polyester resin and its application |
| 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 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6330522A (en) * | 1986-07-23 | 1988-02-09 | Showa Highpolymer Co Ltd | Production of unsaturated polyester resin of excellent air dryability |
| CN102060985A (en) * | 2010-12-17 | 2011-05-18 | 常州华科树脂有限公司 | Unsaturated polyester resin for sheet or bulk molding compound and preparation method thereof |
| CN102174176A (en) * | 2011-03-11 | 2011-09-07 | 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 |
| 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 |
| CN105482087A (en) * | 2015-12-28 | 2016-04-13 | 肇庆福田化学工业有限公司 | Anti-yellowing unsaturated polyester resin and synthetic method thereof |
-
2016
- 2016-06-25 CN CN201610482500.2A patent/CN105906792B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6330522A (en) * | 1986-07-23 | 1988-02-09 | Showa Highpolymer Co Ltd | Production of unsaturated polyester resin of excellent air dryability |
| CN102060985A (en) * | 2010-12-17 | 2011-05-18 | 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 |
| CN102174176A (en) * | 2011-03-11 | 2011-09-07 | 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 |
| CN105482087A (en) * | 2015-12-28 | 2016-04-13 | 肇庆福田化学工业有限公司 | Anti-yellowing unsaturated polyester resin and synthetic method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108503757A (en) * | 2018-02-12 | 2018-09-07 | 嘉兴市新大陆机电有限公司 | A kind of VPI impregnation technologies low viscosity unsaturated polyester resin and its application |
| 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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| CN105906792B (en) | 2017-10-27 |
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