CN1034279C - Method for preparaing dicyclc pentylene modified unsaturated polyester - Google Patents
Method for preparaing dicyclc pentylene modified unsaturated polyester Download PDFInfo
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- CN1034279C CN1034279C CN92101614A CN92101614A CN1034279C CN 1034279 C CN1034279 C CN 1034279C CN 92101614 A CN92101614 A CN 92101614A CN 92101614 A CN92101614 A CN 92101614A CN 1034279 C CN1034279 C CN 1034279C
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Abstract
The present invention discloses a new method for preparing dicyclopentadiene modified unsaturated polyester, which comprises the following steps: (1), carrying out esterification reaction under a shielding gas atmosphere of nitrogen gas within 160 to 205DEGC until an acid value reaches 50 to180 milligrams of potassium hydroxide / gram; (2), cooling to 110 to 140DEGC, and then, dropping a catalyst and dicyclopentadiene to carry out addition reaction; (3), when a system acid value is above 50 milligrams of potassium hydroxide / gram after the addition reaction is completed, gradually rising in temperature to 205 DEG C until the system acid value reaches 40 to 50 milligrams of potassium hydroxide / gram. The water resistance, the acid base resistance and all kinds of physical performance of the dicyclopentadiene modified unsaturated polyester are obviously improved. The dicyclopentadiene modified unsaturated polyester is suitable for coatings, etc.
Description
The invention belongs to the preparation method of dicyclic pentylene modified unsaturated polyester.
As everyone knows, can prepare unsaturated polyester by dibasic alcohol and unsaturated dicarboxylic acid (or acid anhydride) and saturated dicarboxylic acid (or acid anhydride), and unsaturated polyester can with the copolymerization of monomer ethylene based compound.But this product that makes only is suitable for making multiple glass fiber reinforced plastics product, be not suitable for as coating, because when the multipolymer of being made up of unsaturated polyester, vinyl monomer, organo-peroxide and promotor is used for thin layer, can be subjected to the influence of atmosphericoxygen and causes the sticking hand of product surface and solidify not exclusively.
Have now found that, above-mentioned unsaturated polyester is after dicyclic pentylene modified, the multipolymer of itself and vinyl monomer just can not be subjected to the influence of oxygen in the atmosphere, has good air-drying property, and heat-resisting, water-fast and acid and alkali-resistance ability is better than unmodified unsaturated polyester resin.
At present, the method with dicyclic pentylene modified unsaturated polyester has three classes.1, the acid catalysis additive process [is seen document W.Meyer, Hydrocarbon Processing 55,235-238 (1976)], its unstable properties of polyester that makes with this method, the volumetric shrinkage of resin is big, poor heat resistance, and the more unmodified unsaturated polyester resin of mechanical mechanics property (tensile strength, flexural strength, compressive strength and hardness) is low, and the goods fragility that it makes is big, and this is fatal weakness.Tracing it to its cause, mainly is owing to when about 250～280 milligrams of potassium hydroxide/gram of system acid number, add dicyclopentadiene to reaction system, makes molecular weight of polyesters lower, and uneven.2, diene additive process (the same first kind of citing document), the polyester weakness that obtains with this method are the active low of it and vinyl monomer copolymerization, cause product surface to be clamminess, and solidify not exclusively.Trace it to its cause, mainly be under the high temperature more than 160 ℃, to drip dicyclopentadiene to system, cause dicyclopentadiene to be decomposed into cyclopentadiene, and the Diels-Alder addition reaction takes place in the two keys in cyclopentadiene and the polyester molecule chain, make and to reduce natural crosslinking reaction decline with the double key number of vinyl monomer copolymerzation with cross-linking.3, hydrolyzed addition process ［ is seen document D.L.Nelson, modern Plastics, 92-93 (1978)], although the polyester that these class methods make itself and vinyl monomer copolymerization is active high, the air-drying property of goods is good, but its color and luster is dark, and initial reaction stage is a strong exothermal reaction, react restive, this method is difficult for promoting.The preparation technology that United States Patent (USP) 4029848 and the 3347806 and the 1st class and the reaction of the 2nd class are mentioned, its method is the first step unsaturated dicarboxylic acid (or acid anhydride), saturated dicarboxylic acid (or acid anhydride), dibasic alcohol and dicyclopentadiene is dropped into reactor simultaneously, carries out addition reaction under 140 ℃ being lower than; Second step was after addition reaction is finished reaction mixture to be heated to more than 160 ℃, till pet reaction is finished.Because the control of reaction system acid number is improper, the reactant quality product is not good.
The objective of the invention is to propose a kind of dicyclic pentylene modified unsaturated polyester of using, adopt the control differing temps, add dicyclopentadiene when making reaction system reach different acidity, thus the preparation method that the reactant product performance are improved.
The object of the present invention is achieved like this, with the preparation method of dicyclic pentylene modified unsaturated polyester, comprising:
(1) unsaturated dicarboxylic acid (or acid anhydride), saturated dicarboxylic acid (or acid anhydride) and dibasic alcohol are dropped into reactor by proportioning, under nitrogen protection atmosphere, progressively heat up,, reach 50～180 milligrams of potassium hydroxide/gram until acid number 160～205 ℃ of interval reactions.
(2) temperature of reaction system is reduced to 110～140 ℃, drip catalyzer and dicyclopentadiene to system, carry out addition reaction, the general time is 0.5～3.0 hour;
(3) after addition reaction is finished, when the system acid number is higher than 50 milligrams of potassium hydroxide/gram, progressively be warming up to 205 ℃ again, reach 40～50 milligrams of potassium hydroxide/gram until system's acid number.
Wherein each reactant ratio and processing condition are:
Unsaturated dicarboxylic acid (or acid anhydride)/saturated dicarboxylic acid (or acid anhydride) is 1: 1 (mol ratio),
Total carboxylic acid's (or total acid anhydride) is 1: 1.05～1.1 with the dibasic alcohol mol ratio;
Total carboxylic acid's (or total acid anhydride) is 1: 0.05～0.25 with the dicyclopentadiene mol ratio;
When dripping dicyclopentadiene, the reactive system acid number should be 50～180 milligrams of potassium hydroxide/gram, and dicyclopentadiene drips the time and the insulation reaction time is 0.5～3.0 hour, i.e. the addition reaction time is 0.5～3.0 hour;
The catalyzer add-on is 0～0.06% (by weight polyester);
Unsaturated dicarboxylic acid (or acid anhydride) comprises toxilic acid, fumaric acid, methylfumaric acid and composition thereof;
Saturated dicarboxylic acid (or acid anhydride) comprises phthalic acid, terephthalic acid, m-phthalic acid, hexanodioic acid, sebacic acid, Na Dike acid and tetrachlorophthalic anhydride etc.;
Dibasic alcohol comprises ethylene glycol, propylene glycol, glycol ether, dipropylene glycol or its mixture etc.;
The dicyclopentadiene concentrate, it contains 85～95% dicyclopentadiene, can be from the by product C 5 fraction of coal tar or petroleum cracking system ethene;
Unsaturated polyester and dicyclopentadiene addition reaction, catalyzer can be used sulfuric acid, hydrochloric acid and phosphoric acid etc.
With dicyclic pentylene modified unsaturated polyester and vinyl compound copolymerization, its weight ratio is 7: 3-6: 4, catalyzer is an organo-peroxide, as: benzoyl peroxide, methylethyl ketone peroxide, cyclohexanone peroxide etc., promotor is naphthoic acid cobalt, cobalt octoate and xylidine etc., copolymerization is in room temperature or carry out under the high-temperature slightly, promptly carry out the form of construction work of available roll-in, showering or dipping 20-100 ℃ of scope.
Preparation method's of the present invention maximum characteristics are the esterifications of carrying out acid and alcohol earlier, when acid number reaches 50-180 milligram potassium hydroxide/gram, just grand temperature drips dicyclopentadiene during to 110-140 ℃, to control the polyreaction molecular weight and the degree of crosslinking of appropriateness, quality product is significantly improved.
The total carboxylic acid of esterification (or total wine) is 1 with dibasic alcohol mol ratio the best: 1.05-1.10; Total carboxylic acid's (or total acid anhydride) is 1 with mol ratio the best of dicyclopentadiene: 0-0.05-0.25, the amount of dicyclopentadiene is too big, polyester that makes and vinyl monomer be copolymerzation with cross-linking not, performance is bad, when dripping dicyclopentadiene, the reaction system acid number can not be too big, and it is too little not blame molecular weight of polyesters, and uneven, product performance are just bad; The catalyzer of the described unsaturated polyester of existing document west dicyclo diene addition reaction is sulfuric acid and hydrochloric acid etc., and the present invention finds to use phosphoric acid, and effect adds most, the quality product the best that draws, and use the described sulfuric acid of document, and the reactant product colour that obtains is dark, and quality is not good.
The present invention compared with prior art has following significant advantage:
(1) has good water-fast, acidproof and alkali proof ability.
(2) has good thermotolerance.
(3) water-intake rate of its goods and volumetric shrinkage are lower.
(4) surface gloss of its goods and air-drying property are good.
(5) has the favorable mechanical mechanical property.
(6) glass fibre and steel had good adhesive power.
Specify characteristics of the present invention and advantage with three embodiment below.
Example 1:
The maleic anhydride of 68.6g, 103.6g phthalic anhydride and the propylene glycol of 112.8g pack into and have agitator, protractor, in the four-hole boiling flask of fractionation loading amount and N2 ingress pipe, flow down at N2 and to be warming up to 160 ℃ lentamente, insulation was given poly-30 minutes under this temperature, 180-190 ℃ of interval continued to be warming up to lentamente in the back, insulation reaction to system's acid number reaches 140-160[mgKOH/g] time be cooled to 120-130 ℃ rapidly, under this temperature, drip the dicyclopentadiene of 30.85g, in 1 hour, drip off, and insulation reaction 1 hour again, after slowly be warming up to 200 ± 5 ℃, reach till 40 ± 2 until endpoint acid number, promptly get dicyclic pentylene modified unsaturated polyester.
65 parts polyester are dissolved in 35 parts the vinylbenzene and are unsaturated polyester resin, under naphthoic acid cobalt (1% concentration) catalysis of 4 parts cyclohexanone peroxides (50% concentration) and four parts, but the glass fiber reinforced plastics product of room temperature preparation various uses also can be made the coating purposes.Its various performances 1-table 3 of relatively seeing attached list.
Example 2:
The propylene glycol of the phthalic anhydride of the maleic anhydride of 39.2g, 59.2g and 65.7g is dropped into the device of example 1, flow down at N2 and to be warmed up to 160 ℃ lentamente, insulation was given poly-30 minutes, the back continues to be warming up to 200 ± 5 ℃ lentamente, acid number reaches 50 ± 2[mgKOH/g until system] time be cooled to 125-135 ℃ rapidly, under this temperature, add the phosphoric acid of 35mg, and in 1 hour, be added dropwise to the dicyclopentadiene of 12.7g, continue insulation reaction and get final product stopped reaction after 2 hours, promptly get dicyclic pentylene modified unsaturated polyester, subsequent operations is with example 1.Its various performances 1-table 3 of relatively seeing attached list.
Example 3:
The maleic anhydride of 68.6g, 103.6g phthalic anhydride and the propylene glycol of 117.04g drop into the device of example 1, flow down at N2 and to be warming up to 160 ℃ lentamente, insulation was given poly-30 minutes, the follow-up continuous 190-200 ℃ of interval that be warming up to, acid number reaches 80-100[mgKOH/g until system] time be cooled to 120-130 ℃ rapidly, under this temperature, add the phosphoric acid of 111.5mg, and in 1 hour, be added dropwise to the dicyclopentadiene of 14.8g, continued insulation reaction 0.5 hour, after slowly be warming up to 200 ± 5 ℃, reach till 40 ± 2 until endpoint acid number, promptly get dicyclic pentylene modified unsaturated polyester, subsequent operations is with example 1.Various performances slightly.Attached: the testing method of every performance index:
The sample of the inventive method preparation under equal conditions records between the while by identical testing method with domestic best brand of product (Changzhou 253 191# of factory resins).
1, the acid number of resin is pressed the standard test of GB2895-82.
2, the viscosity of resin is scaled Pa.s unit with being coated with 4 glasss of mensuration by identical method.
3, the proportion of resin is pressed the GB1463-78 standard test.
4, the water-intake rate of casting matrix (%) is pressed the GB1462-78 standard test.
5, the volumetric shrinkage of resin is pressed density difference mensuration.
6, the gelation time of resin is pressed the GB7193.6-87 standard test
7, self-vulcanizing time and exothermic peak temperature.
Solidify proportioning: portions of resin initiator: promotor=100: 4: 4 (weight)
Initiator-the contain cyclohexanone peroxide of 50% dibutyl phthalate.
Promotor-the contain styrene solution of 1% cobalt naphthenate.
Definition: under the condition of 25 ℃ of room temperatures, resin is from adding promotor, and self temperature rises till reaching the highest exothermic temperature, and required time is defined as the self-vulcanizing time, and the highest exothermic temperature that is reached is defined as the room temperature exothermic peak temperature.
8, the tension of casting matrix, resistance to compression, resistance to bend are pressed GB2567-2571-81 standard test specimen preparation condition: solidify proportioning with " 7 ", at room temperature solidified 24 hours, 80 ℃ of following thermal treatment 5 hours.
9, Ba Ke hardness is pressed the GB3854-83 standard test.Ba Ke sclerometer system uses the HBa-1 type, is equivalent to U.S. model GyzT934-1 Ba Ke sclerometer.
10, resistance to chemical corrosion is pressed the standard test of GB3857-83.
11, the oven test of casting matrix.
Solidify proportioning with " 7 ", at room temperature solidified 24 hours, the back is carried out heat-resisting mensuration on request in the thermostat container of temperature control.
The physicochemical property of table 1, resin and the mechanical mechanics property of casting matrix
The oven test of table 2, casting resin (weight loss %)
* mean the product of Changzhou 253 factories.Each system of parameters under equal conditions records simultaneously by same procedure.
Table 3, resistance to chemical corrosion (changes in weight %)
Claims (4)
1, a kind of method for preparing dicyclic pentylene modified unsaturated polyester, comprising:
(1) unsaturated dicarboxylic acid or acid anhydride, saturated dicarboxylic acid or acid anhydride and dibasic alcohol are dropped into reactor by proportioning, under nitrogen protection atmosphere, progressively heat up,, reach 50～180 milligrams of potassium hydroxide/gram until acid number 160～205 ℃ of interval reactions;
(2) temperature of reaction system is reduced to 110 ℃～140 ℃, drip catalyzer and dicyclopentadiene to system, carry out addition reaction, the reaction times is 0.5～3.0 hour;
When (3) the system acid number is higher than 50 milligrams of potassium hydroxide/gram after addition reaction is finished, progressively be warming up to 205 ℃ again, reach 40～50 milligrams of potassium hydroxide/gram until the system acid number;
Wherein each reactant ratio is as follows:
The mol ratio of unsaturated dicarboxylic acid or acid anhydride and saturated dicarboxylic acid or acid anhydride is 1: 1; The mol ratio of total carboxylic acid or total acid anhydride and dibasic alcohol is 1: 1.05～1.10; The mol ratio of total carboxylic acid or total acid anhydride and dicyclopentadiene is 1: 0.05～0.25; The catalyzer add-on is 0～0.06% (by the polyester gross weight).
2, preparation method according to claim 1 is characterized in that catalyzer adopts phosphoric acid.
3, preparation method according to claim 1, it is characterized in that when total acid or total acid anhydride and dibasic alcohol mol ratio are 1: 1.06, carry out esterification, 160 ℃ of pre-polymerizations 30 minutes, be warming up to 180～190 ℃ of reactions again, reach 140～160 milligrams of potassium hydroxide/gram until system's acid number, be cooled to 120～130 ℃ rapidly, under this temperature, drip dicyclopentadiene, its amount is 1: 0.17 in total acid or total acid anhydride and dicyclopentadiene mol ratio, dripped 1 hour and the insulation reaction time is 1 hour, after slowly be warming up to 200 ± 5 ℃, be 40 ± 2 milligrams of potassium hydroxide/gram until endpoint acid number.
4, preparation method according to claim 1 and 2, it is characterized in that total acid or total acid anhydride and dibasic alcohol mol ratio are 1: 1.08, esterification was carried out 30 minutes at 160 ℃, follow-up continuing is warming up to 200 ± 5 ℃, when system's acid number reaches 50 ± 2 milligrams of hydrogen potassium hydride KHs/gram, reduce to 125～135 ℃ rapidly, add 0.025% phosphoric acid and drip dicyclopentadiene in this temperature, its amount is 1: 0.12 by mol ratio of total acid or total acid anhydride and dicyclopentadiene, drips 1 hour and insulation reaction is 2 hours.
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| Application Number | Priority Date | Filing Date | Title |
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| CN92101614A CN1034279C (en) | 1992-03-07 | 1992-03-07 | Method for preparaing dicyclc pentylene modified unsaturated polyester |
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| CN92101614A CN1034279C (en) | 1992-03-07 | 1992-03-07 | Method for preparaing dicyclc pentylene modified unsaturated polyester |
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| CN1070657A CN1070657A (en) | 1993-04-07 |
| CN1034279C true CN1034279C (en) | 1997-03-19 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1056388C (en) * | 1996-10-03 | 2000-09-13 | 中国石化扬子石油化工公司 | Preparation method of dicyclopentadiene modified unsaturated polyester resin |
| CN100482713C (en) * | 2005-06-17 | 2009-04-29 | 中国石化上海石油化工股份有限公司 | Dicyclopentadiene modified unsaturated polyester resin preparation method |
| CN102206310A (en) * | 2011-04-22 | 2011-10-05 | 常州华科树脂有限公司 | Vacuum lead-in unsaturated polyester resin for fan blade and preparation method thereof |
| CN102659649A (en) * | 2012-04-17 | 2012-09-12 | 黑龙江省科学院大庆分院 | Method for synthesis of polyfunctional dicyclopentadienyl ether |
| CN109679032A (en) * | 2018-12-11 | 2019-04-26 | 成都杰晟蜀邦新材料科技有限公司 | A kind of easy to polish unsaturated polyester resin of high clear high levelling and preparation method |
| CN114437332B (en) * | 2022-03-11 | 2023-09-19 | 三河亮克威泽工业涂料有限公司 | Polyester oligomer and preparation method thereof, photo-curing putty and preparation method, curing method and application thereof |
| CN115181220B (en) * | 2022-09-13 | 2022-12-09 | 山东旺林新材料有限公司 | Preparation method and application of p-benzene type unsaturated polyester resin |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0166453A2 (en) * | 1984-06-29 | 1986-01-02 | Union Carbide Corporation | A process for producing low viscosity curable polyester resin compositions |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0166453A2 (en) * | 1984-06-29 | 1986-01-02 | Union Carbide Corporation | A process for producing low viscosity curable polyester resin compositions |
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