CN101570589A - Method for preparing environment-friendly unsaturated polyester resin and product and application thereof - Google Patents
Method for preparing environment-friendly unsaturated polyester resin and product and application thereof Download PDFInfo
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- CN101570589A CN101570589A CNA2008102050067A CN200810205006A CN101570589A CN 101570589 A CN101570589 A CN 101570589A CN A2008102050067 A CNA2008102050067 A CN A2008102050067A CN 200810205006 A CN200810205006 A CN 200810205006A CN 101570589 A CN101570589 A CN 101570589A
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Abstract
The invention relates to a method for preparing environment-friendly unsaturated polyester resin, and a product and application thereof. The method for preparing the environment-friendly o-benzene type unsaturated polyester resin comprises that: in the presence of an inhibiting agent, unsaturated dicarboxylic acid, aliphatic or aromatic dicarboxylic acid or anhydride of the aliphatic or aromatic dicarboxylic acid, and polyhydric alcohol are used as a reaction system; after reaction, a reaction monomer is added in the reaction system for dilution so as to prepare unsaturated resin; and in the reaction system, the mol percentage of the three components is: 15 to 20mol percent of the unsaturated dicarboxylic acid, 25 to 35mol percent of the aliphatic or aromatic dicarboxylic acid or the anhydride of the aliphatic or aromatic dicarboxylic acid, and 50 to 55mol percent of the polyhydric alcohol, wherein the aliphatic or aromatic dicarboxylic acid or the anhydride of the aliphatic or aromatic dicarboxylic acid at least comprises one or two of phthalic acid and phthalic anhydride. The environment-friendly o-benzene type unsaturated polyester resin product prepared by the method is the o-benzene unsaturated polyester resin, of which the viscosity is between 800 and 1,200MPa.s and the number-average molecular weight is between 1,700 and 2,500. The product can be used for producing environment-friendly buttons and has passed EU environmental protection tests.
Description
Technical field
The present invention relates to the preparation method and products thereof and the purposes of environment-friendly unsaturated polyester resin, particularly the unsaturated polyester resin base product that can detect by European Union environmental protection also relate to the purposes of resin in button.In addition, the invention still further relates to the production method of this unsaturated polyester resin.
Background technology
In the prior art, can adopt the metaphenylene resin mostly by the unsaturated polyester resin of the firm up-to-date environmental protection act of issuing of European Union in 2008, but this kind resin cost is higher, the market acceptance is poor, and the metaphenylene production of resins cycle is longer, product colour also not too can satisfy the system button requirement.Therefore, it is good to press for a kind of color on the market, the adjacent benzene type unsaturated polyester product that price has superiority again.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method who produces the adjacent benzene unsaturated polyester resin of environment-friendly type that can pass through the up-to-date environmental protection act of European Union in 2008.
Another technical problem to be solved by this invention is to provide a kind of adjacent benzene unsaturated polyester resin of environment-friendly type product that obtains at above-mentioned preparation method.
A technical problem more to be solved by this invention is to provide the purposes of the adjacent benzene unsaturated polyester resin of a kind of above-mentioned environment-friendly type product.
The present invention solves the problems of the technologies described above the technical scheme of being taked: the preparation method that the adjacent benzene unsaturated polyester resin of a kind of environment-friendly type is provided, in the presence of the inhibitor toluhydroquinone, with unsaturated dicarboxylic acid, aliphatics or aromatic dicarboxylic acid and polyvalent alcohol is reaction system, comprise the adding reaction monomers after the reaction, make unsaturated polyester, wherein, in reaction system, the molar content of three components is:
Unsaturated dicarboxylic acid 15～20mol%
Aliphatics or aromatic dicarboxylic acid or its acid anhydrides 25～35mol%
Polyvalent alcohol 50～55mol%,
Described aliphatics or aromatic dicarboxylic acid or its acid anhydrides comprise one or both in phthalic acid, the Tetra hydro Phthalic anhydride at least.
On the such scheme basis, described unsaturated dicarboxylic acid is one or more in toxilic acid, maleic anhydride, the fumaric acid, preferred maleic anhydride;
Described aliphatics or aromatic dicarboxylic acid or acid anhydrides also comprise one or both in hexanodioic acid, the sebacic acid, are preferably the combination of Tetra hydro Phthalic anhydride and hexanodioic acid;
Described polyvalent alcohol is 1,2-propylene glycol, 1,3 propylene glycol, 1,4-butyleneglycol, 1, two or more in 6-hexylene glycol, neopentyl glycol, ethylene glycol, Diethylene Glycol, dipropylene glycol, the glycerine.The preferred weathering resistance of polyvalent alcohol, the polyvalent alcohol of anti-good impact resistance, most important to cured article, preferred 1,2-propylene glycol, 1, two or more in ammediol, neopentyl glycol, ethylene glycol, Diethylene Glycol, the dipropylene glycol; Further optimum condition is: polyvalent alcohol comprises propylene glycol at least, and the amount of propylene glycol is not less than the 25mol% of reaction system molar percentage.
Preferred 16～the 18mol% of the consumption of unsaturated dicarboxylic acid is specifically as follows 16,16.5,17,17.5 or 18mol%; Preferred 27～the 31mol% of the consumption of aliphatics or aromatic dicarboxylic acid is specifically as follows 27,28,29,30 or 31mol%; The consumption of polyvalent alcohol is specifically as follows 50,51, and 52,53,54 or 55mol%.
On the basis of such scheme, the consumption of described inhibitor (or claiming stopper) Resorcinol is 30～40ppm of reaction system weight.
The concrete preparation method of the adjacent benzene type unsaturated polyester resin of environmental protection comprises the steps:
The first step: in the presence of the inhibitor toluhydroquinone, unsaturated dicarboxylic acid and polyvalent alcohol are warming up to 190～200 ℃ of reactions;
Second step: the question response acid number is cooled to 140～150 ℃ after being lower than 100mgKOH/g (preferably being lower than 80mgKOH/g), adds aliphatics or aromatic dicarboxylic acid or anhydride reaction;
The 3rd step: the question response acid number is reduced to 25～35mgKOH/g, and (preferred 28～31mgKOH/g) backs add Resorcinol, are cooled to 120～140 ℃, add the reaction monomers dilution earlier, add softening agent and paraffin again, make unsaturated polyester.
On the basis of such scheme, in the 3rd step, can vacuumize when needing, vacuumize and reduced to 25～35mgKOH/g to acid number in 2～3 hours, remove the water that produces in the reaction by separator between the reaction period.
In above-mentioned the 3rd step, the consumption of described Resorcinol is 30～40ppm of reaction system weight.
In above-mentioned the 3rd step, described reaction monomers is one or both in vinylbenzene, the methacrylic ester, and the consumption of reaction monomers is 30～35% of a reaction system weight.Preferable amount is 31～33%, is specifically as follows 31,31.5,32,32.5 or 33%.
In above-mentioned the 3rd step, described softening agent is one or more in ATBC, Octyl adipate, dibutyl maleate, dioctyl maleate, Uniflex DBS, dioctyl sebacate, phosphate toluene diphenyl ester, butyl oleate, the alpha-methyl styrene, and plasticizer dosage is 0.5～5% of a reaction system weight.Be specifically as follows 0.5,1,1.5,2,2.5,3,3.5,4,4.5 or 5%.
In the preferred ATBC of softening agent, Octyl adipate, dibutyl maleate, dioctyl maleate, the dioctyl sebacate one or more.The unexpected discovery, do not collapse the limit performance for obtaining quick punching out button blank, the environment-friendly type softening agent Octyl adipate that adds in adjacent benzene unsaturated polyester resin preparation, dioctyl sebacate and dioctyl maleate mix the shock resistance that use can improve the button goods.
In above-mentioned the 3rd step, the consumption of described paraffin is 0.05～0.06% of a reaction system weight, is specifically as follows 0.05,0.055 or 0.06%.
The present invention is directed to the adjacent benzene unsaturated polyester resin of the environment-friendly type product that above-mentioned preparation method makes, be adjacent benzene unsaturated polyester resin, its viscosity is 800～1200mPas, and number-average molecular weight is 1700～2500.
The invention provides the purposes of the adjacent benzene type of a kind of environmental protection unsaturated polyester resin product, be used to prepare the environment-friendly type button.
Described unsaturated polyester resin can be with conventional unsaturated promotion system, and as the combination of solidifying agent cobalt iso-octoate and initiator MEKP, or cyclohexanone peroxide or known other solidifying agent are cured.
Resin after the curing send third party authority feeler mechanism, and (BUREAU VERITAS INTERTEK) detects, and every environmental requirement can both be up to standard.
Need extra impact property as cured article, can in the preparation process of adjacent benzene unsaturated polyester resin, increase softening agent Octyl adipate, the amount of maleic dioctyl ester; Keep suitable viscosity can reduce the consumption of reaction monomers as need, can keep this resin when the system button, to keep the favorable manufacturability energy simultaneously.
The invention has the beneficial effects as follows:
Adjacent benzene unsaturated polyester resin of the present invention embodies the favorable manufacturability energy when the system button, comprise the levelling property of pearlite slurry in resin, punching out button blank does not collapse the limit performance fast, and weathering resistance, environment-friendly type softening agent Octyl adipate, dioctyl sebacate and dioctyl maleate mix the shock resistance that use can improve the button goods.
Embodiment
Embodiment 1
The preparation of the adjacent benzene unsaturated polyester resin of environment-friendly type A:
The first step: in the presence of the inhibitor toluhydroquinone, 0.17mol maleic anhydride, 0.28mol propylene glycol, 0.08mol ethylene glycol and 0.15mol Diethylene Glycol mix, and are warming up to 195 ℃ of reactive polymerics;
Second step: the question response acid number is cooled to 140 ℃ after being lower than 100mgKOH/g, adds the reaction of 0.30mol Tetra hydro Phthalic anhydride and 0.01mol hexanodioic acid;
The 3rd step: vacuumize after 2～3 hours question response acid numbers reduce to 28～31mgKOH/g, the Resorcinol that all adds 30ppm in reaction system weight, be cooled to 130 ℃, the vinylbenzene of adding 30% dilution earlier, add 1% ATBC (ATBC) and 52～54 ° of paraffin of 0.05% again, make the adjacent benzene unsaturated polyester resin of environment-friendly type A.
The viscosity of gained resin is at 950mPas (25 ℃), and gel time was at 3 minutes 40 seconds～4 minutes (1% cobalt iso-octoate solution, 1% initiator MEKP).
The application of the adjacent benzene unsaturated polyester resin of environment-friendly type A:
The unsaturated polyester resin A of preparation is solidified with initiator 1%MEKP and solidifying agent cobalt iso-octoate, and mechanical property and third party's detected result are as shown in table 1.
Table 1
| Interventions Requested | Assay | Test basis |
| Tensile strength MPa | 60.8 | GB/T2568 |
| Modulus in tension GPa | 2.66 | GB/T2568 |
| Tension set % | 3.68 | GB/T2568 |
| Flexural strength MPa | 89.7 | GB/T2570 |
| Bending elastic modulus GPa | 2.87 | GB/T2570 |
| Impelling strength KJ/m 2 | 13.12 | GB/T2571 |
| Heat-drawn wire ℃ | 55 | GB/T1634.2 |
| The phthalate ∑ | N.D | BVCPS in house method(LCMSD) |
| Heavy metal content | N.D | EN 71.part III ASTM F963 |
Embodiment 2
The preparation of the adjacent benzene unsaturated polyester resin of environment-friendly type B:
The first step: in the presence of the inhibitor toluhydroquinone, 0.18mol maleic anhydride, 0.11mol neopentyl glycol, 0.25mol propylene glycol and 0.15mol Diethylene Glycol mix, and are warming up to 195 ℃ of reactive polymerics;
Second step: the question response acid number is cooled to 140 ℃ after being lower than 80mgKOH/g, adds the 0.31mol phthalic anhydride;
The 3rd step: vacuumize 2～3 hours question response acid numbers and reduce to and add the 40ppm Resorcinol behind 28～31mgKOH/g, be cooled to 130 ℃, the vinylbenzene of adding 28% dilution earlier, add 1% Octyl adipate again, 2% dioctyl maleate, 1% alpha-methyl styrene and 52～54 ° of paraffin of 0.055% make the adjacent benzene unsaturated polyester resin of environment-friendly type A.
The viscosity of gained resin is at 900mPas (25 ℃), and gel time is at 3 minutes 40 seconds～4 minutes (1% cobalt iso-octoate solution, 1% initiator MEKP), according to the gpc analysis molecular weight at Mn ≈ 2100, Mw ≈ 4800.
The application of the adjacent benzene unsaturated polyester resin of environment-friendly type B:
The unsaturated polyester resin B of preparation is solidified with initiator 1%MEKP and solidifying agent cobalt iso-octoate, and mechanical property and third party's detected result are as shown in table 2.
Table 2
| Interventions Requested | Assay | Test basis |
| Tensile strength MPa | 56.7 | GB/T2568 |
| Modulus in tension GPa | 2.54 | GB/T2568 |
| Tension set % | 15.95 | GB/T2568 |
| Flexural strength MPa | 86.4 | GB/T2570 |
| Bending elastic modulus GPa | 2.63 | GB/T2570 |
| Impelling strength KJ/m2 | 30.08 | GB/T2571 |
| Heat-drawn wire ℃ | 54.3 | GB/T1634.2 |
| The phthalate ∑ | N.D | BVCPS in house method(LCMSD) |
| Heavy metal content | N.D | EN 71.part III ASTM F963 |
Embodiment 3
The preparation of the adjacent benzene unsaturated polyester resin of environment-friendly type C:
The first step: in the presence of the inhibitor toluhydroquinone, 0.172mol maleic anhydride, 0.011mol dipropylene glycol, 0.394mol propylene glycol and 0.032mol Diethylene Glycol, 0.083mol ethylene glycol mix, and are warming up to 195 ℃ of reactive polymerics;
Second step: the question response acid number is cooled to 140 ℃ after being lower than 80mgKOH/g, adds the 0.305mol phthalic anhydride;
The 3rd step: vacuumize 2～3 hours question response acid numbers and reduce to and add the 40ppm Resorcinol behind 28～31mgKOH/g, be cooled to 130 ℃, the vinylbenzene of adding 28% dilution earlier, add 1% Octyl adipate again, 2% dioctyl maleate, 1% dioctyl sebacate and 52～54 ° of paraffin of 0.06% make the adjacent benzene type of environmental protection unsaturated polyester resin C.
The viscosity of gained resin is at 1050mPas (25 ℃), and gel time is at 4 minutes 30 seconds～5 minutes (1% cobalt iso-octoate solution, 1% initiator MEKP), according to the gpc analysis molecular weight at Mn ≈ 2250, Mw ≈ 4950.
The application of the adjacent benzene unsaturated polyester resin of environment-friendly type C:
The unsaturated polyester resin C of preparation is solidified with initiator 1%MEKP and solidifying agent cobalt iso-octoate, and mechanical property and third party's detected result are as shown in table 3.
Table 3
| Interventions Requested | Assay | Test basis |
| Tensile strength MPa | 63.5 | GB/T2568 |
| Modulus in tension GPa | 2.85 | GB/T2568 |
| Tension set % | 8.95 | GB/T2568 |
| Flexural strength MPa | 98.7 | GB/T2570 |
| Bending elastic modulus GPa | 3.56 | GB/T2570 |
| Impelling strength KJ/m2 | 11.5 | GB/T2571 |
| Heat-drawn wire ℃ | 60.5 | GB/T1634.2 |
| The phthalate ∑ | N.D | BVCPS in house method(LCMSD) |
| Heavy metal content | N.D | EN 71.part III ASTM F963 |
Annotate: table 1, the phthalate ∑ in 2,3 detects representative office for third party feeler mechanism: Shen, Shanghai US business's product detection company limited.
Claims (10)
1, the preparation method of the adjacent benzene type of a kind of environmental protection unsaturated polyester resin, in the presence of inhibitor, with unsaturated dicarboxylic acid, aliphatics or aromatic dicarboxylic acid or its acid anhydrides and polyvalent alcohol is reaction system, comprise after the reaction and add the reaction monomers dilution, make unsaturated polyester, it is characterized in that: in reaction system, the molar content of three components is:
Unsaturated dicarboxylic acid 15～20mol%
Aliphatics or aromatic dicarboxylic acid or acid anhydrides 25～35mol%
Polyvalent alcohol 50～55mol%,
Wherein, aliphatics or aromatic dicarboxylic acid or acid anhydrides comprise one or both in phthalic acid, the Tetra hydro Phthalic anhydride at least.
2, the preparation method of the adjacent benzene type of environmental protection according to claim 1 unsaturated polyester resin, it is characterized in that: described unsaturated dicarboxylic acid is one or more in toxilic acid, maleic anhydride, the fumaric acid; Described aliphatics or aromatic dicarboxylic acid or acid anhydrides also comprise one or both in hexanodioic acid, the sebacic acid; Described polyvalent alcohol is 1,2-propylene glycol, 1,3 propylene glycol, 1,4-butyleneglycol, 1, two or more in 6-hexylene glycol, neopentyl glycol, ethylene glycol, Diethylene Glycol, dipropylene glycol, the glycerine.
3, the preparation method of the adjacent benzene type of environmental protection according to claim 1 and 2 unsaturated polyester resin is characterized in that comprising the steps:
The first step: in the presence of the inhibitor toluhydroquinone, unsaturated dicarboxylic acid and polyvalent alcohol are warming up to 190～200 ℃ of reactions;
Second step: the question response acid number is cooled to 140～150 ℃ after being lower than 100mgKOH/g, adds aliphatics or aromatic dicarboxylic acid or anhydride reaction;
The 3rd step: the question response acid number adds Resorcinol after reducing to 25～35mgKOH/g, is cooled to 120～140 ℃, adds the reaction monomers dilution earlier, adds softening agent and paraffin again, makes unsaturated polyester.
4, the preparation method of the adjacent benzene type of environmental protection according to claim 3 unsaturated polyester resin is characterized in that: in the 3rd step, vacuumize and reduced to 25～35mgKOH/g to acid number in 2～3 hours, remove the water that produces in the reaction by separator between the reaction period.
5, the preparation method of the adjacent benzene type of environmental protection according to claim 3 unsaturated polyester resin, it is characterized in that: the consumption of described Resorcinol is 30～40ppm of reaction system weight.
6, the preparation method of the adjacent benzene unsaturated polyester of environment-friendly type according to claim 3, it is characterized in that: described reaction monomers is one or both in vinylbenzene, the methacrylic ester, the consumption of reaction monomers is 30～35% of a reaction system weight.
7, the preparation method of the adjacent benzene type of environmental protection according to claim 3 unsaturated polyester, it is characterized in that: described softening agent is one or more in ATBC, Octyl adipate, dibutyl maleate, dioctyl maleate, Uniflex DBS, dioctyl sebacate, phosphate toluene diphenyl ester, butyl oleate, the alpha-methyl styrene, and plasticizer dosage is 0.5～5% of a reaction system weight.
8, the preparation method of the adjacent benzene type of environmental protection according to claim 3 unsaturated polyester, it is characterized in that: the consumption of described paraffin is 0.05～0.06% of a reaction system weight.
9, the adjacent benzene unsaturated polyester resin of the environment-friendly type product that makes at the described preparation method of one of claim 1 to 8 is adjacent benzene unsaturated polyester resin, and its viscosity is 800～1200mPas, and number-average molecular weight is 1700～2500.
10, at the purposes of the adjacent benzene type of the described environmental protection of claim 9 unsaturated polyester resin product, be used to prepare the environment-friendly type button.
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| CNA2008102050067A CN101570589A (en) | 2008-12-30 | 2008-12-30 | Method for preparing environment-friendly unsaturated polyester resin and product and application thereof |
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| CNA2008102050067A CN101570589A (en) | 2008-12-30 | 2008-12-30 | Method for preparing environment-friendly unsaturated polyester resin and product and application thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805429A (en) * | 2010-03-18 | 2010-08-18 | 上海新天和树脂有限公司 | Flexible unsaturated polyester resin and preparation method and application thereof |
| CN102161734A (en) * | 2011-03-07 | 2011-08-24 | 上海新天和树脂有限公司 | Normal-temperature-cured zero-shrinkage unsaturated polyester resin and preparation method thereof |
| CN102551277A (en) * | 2012-01-09 | 2012-07-11 | 广东溢达纺织有限公司 | Thermo-oxidative aging resistant unsaturated polyester resin button and preparation method thereof |
| CN102585107A (en) * | 2012-03-09 | 2012-07-18 | 宜兴市兴合树脂有限公司 | Unsaturated polyester resin for button and preparation method thereof |
| CN103172844A (en) * | 2011-12-21 | 2013-06-26 | 常州市华润复合材料有限公司 | Unsaturated polyester with low viscosity and application thereof |
| CN103182760A (en) * | 2012-09-24 | 2013-07-03 | 浙江伟星实业发展股份有限公司 | Resin button and production method |
| CN104026812A (en) * | 2014-06-19 | 2014-09-10 | 浙江伟星实业发展股份有限公司 | Preparation method of unsaturated polyester resin buttons |
| CN104650299A (en) * | 2015-01-31 | 2015-05-27 | 宜兴市兴合树脂有限公司 | Unsaturated polyester resin for buttons and preparation method of unsaturated polyester resin |
| CN105968271A (en) * | 2016-06-08 | 2016-09-28 | 浙江德尚化工科技有限公司 | Preparation method of acrylic acid grafted and modified saturated polyester resin |
| CN108359360A (en) * | 2018-03-20 | 2018-08-03 | 牛友正 | A kind of waterproofing agent and its preparation method and application |
| CN109957097A (en) * | 2017-12-25 | 2019-07-02 | 宜兴市兴南复合材料厂有限公司 | A kind of button unsaturated-resin and preparation process |
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2008
- 2008-12-30 CN CNA2008102050067A patent/CN101570589A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101805429A (en) * | 2010-03-18 | 2010-08-18 | 上海新天和树脂有限公司 | Flexible unsaturated polyester resin and preparation method and application thereof |
| CN102161734A (en) * | 2011-03-07 | 2011-08-24 | 上海新天和树脂有限公司 | Normal-temperature-cured zero-shrinkage unsaturated polyester resin and preparation method thereof |
| CN103172844A (en) * | 2011-12-21 | 2013-06-26 | 常州市华润复合材料有限公司 | Unsaturated polyester with low viscosity and application thereof |
| CN102551277A (en) * | 2012-01-09 | 2012-07-11 | 广东溢达纺织有限公司 | Thermo-oxidative aging resistant unsaturated polyester resin button and preparation method thereof |
| CN102585107A (en) * | 2012-03-09 | 2012-07-18 | 宜兴市兴合树脂有限公司 | Unsaturated polyester resin for button and preparation method thereof |
| CN103182760B (en) * | 2012-09-24 | 2014-12-17 | 浙江伟星实业发展股份有限公司 | Resin button and production method |
| CN103182760A (en) * | 2012-09-24 | 2013-07-03 | 浙江伟星实业发展股份有限公司 | Resin button and production method |
| CN104026812A (en) * | 2014-06-19 | 2014-09-10 | 浙江伟星实业发展股份有限公司 | Preparation method of unsaturated polyester resin buttons |
| CN104026812B (en) * | 2014-06-19 | 2016-06-08 | 浙江伟星实业发展股份有限公司 | The preparation method of a kind of unsaturated polyester resin button |
| CN104650299A (en) * | 2015-01-31 | 2015-05-27 | 宜兴市兴合树脂有限公司 | Unsaturated polyester resin for buttons and preparation method of unsaturated polyester resin |
| CN104650299B (en) * | 2015-01-31 | 2018-08-28 | 宜兴市兴合树脂有限公司 | A kind of button unsaturated polyester resin and preparation method thereof |
| CN105968271A (en) * | 2016-06-08 | 2016-09-28 | 浙江德尚化工科技有限公司 | Preparation method of acrylic acid grafted and modified saturated polyester resin |
| CN109957097A (en) * | 2017-12-25 | 2019-07-02 | 宜兴市兴南复合材料厂有限公司 | A kind of button unsaturated-resin and preparation process |
| CN108359360A (en) * | 2018-03-20 | 2018-08-03 | 牛友正 | A kind of waterproofing agent and its preparation method and application |
| CN108359360B (en) * | 2018-03-20 | 2020-12-25 | 牛友正 | Waterproof agent and preparation method and application thereof |
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Application publication date: 20091104 |