CN102181014B - Bi-component flame-retardant low-viscosity unsaturated polyester resin and preparation method thereof - Google Patents
Bi-component flame-retardant low-viscosity unsaturated polyester resin and preparation method thereof Download PDFInfo
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Abstract
The invention relates to bi-component flame-retardant low-viscosity unsaturated polyester resin and a preparation method thereof. The unsaturated polyester resin is prepared by undergoing a polycondensation reaction on dihydric alcohol and binary acid/acid anhydride. A cross-linking agent and a flame retardant are added in the reaction, so that the aims of lowering resin viscosity and enhancing material intensity and flame retardance are fulfilled, and the unsaturated polyester resin can be taken as a grouting reinforcement material for broken surrounding rocks and loose coal-rock masses in underground constructions such as mines and the like.
Description
Technical field
The invention belongs to the polymer materials field, relate to a kind of low viscosity chemistry slip casting strengthening material and complete processing thereof, be specifically related to a kind of bi-component flame-retardant low viscosity unsaturated polyester resin and preparation method thereof.
Background technology
In the underground workss such as mine, tunnel; in the particularly coal mining engineering; often can run into the problem that broken coal and rock and other country rocks need reinforcement, common way is to use the canopy cribbing to support or cooperate resin anchoring agent to carry out its support reinforcement with anchor pole and anchor cable.The resin-bonded mastic that resin anchoring agent generally consists of with fillers such as unsaturated polyester resin and stone flours is as tackiness agent, and as solidifying agent, the protection composite bag made from polyester film is made the powder stick form as wrapping material with benzoyl peroxide.Patent US 4260699 discloses resin anchoring agent and the using method thereof that unsaturated polyester resin and solidifying agent are made, and the method for this resin bolt support has become the topmost method of present colliery tunnel support.
Yet, resin bolt support and shed ding support are in many cases and be not suitable for its support reinforcement of breaking surrounding rock body, at this moment need cement-based material or synthetic resin material are made injection slurry, injection slurry is injected in the slit of breaking surrounding rock body with grouting pump, plays the effect of integral reinforcing after the curing.Cement based slip casting strengthening material such as single liquid grout, cement-silicate slurry and cement clay slip etc. are the slip casting strengthening materials that uses the earliest, these materials owing to inexpensive, safe, nontoxic and preferably induration ultimate compression strength obtained widely to use, but these slurry materials belong to means of particulate material, slurries are difficult to be filled in the tiny crack and go, and application is restricted.The synthetic resin injecting paste material that uses at present comprises urethane, Resins, epoxy, urea-formaldehyde resin, polyacrylic ester and acrylamide etc.Volumetric expansion and viscous deformation had obtained to use more widely in the reinforcing for grouting in coal mine engineering when polyurethanes slip casting strengthening material solidified because of it, but this class material exists, and viscosity is large, infiltration difficulty in the stratum, meet water reaction foaming and cause the defectives such as strength decreased, especially there are stronger toxicity in a large amount of unreacted isocyanic ester and catalyzer, and HUMAN HEALTH and mine safety are brought harm; Urea-formaldehyde resin exists inexpensive, difficult combustion and the little advantage of viscosity, but its adhesiveproperties is relatively poor, concretion body strength is on the low side, and the not enough 10MPa of its ultimate compression strength, and a large amount of formaldehyde is overflowed contaminate environment, infringement HUMAN HEALTH from reinforcing area.Disclose among patent US 3091935 and the US 3091936 with unsaturated polyester resin as slip casting strengthening material, still, these materials exist viscosity greatly, the defective such as not fire-retardant and easy contraction.A kind of method with unsaturated polyester resin grouting and reinforcing ravelly ground has been described among the patent US 5436396, the pearl filler that described unsaturated polyester resin contains more than 15% shrinks with control, resin viscosity reaches 1000mPa.s, and product does not possess flame retardant resistance.Yet these materials are because viscosity is larger, and add the factor such as graininess filler, have difficulties in pumping with when injecting tiny crack.The flame retardant resistance of not having is also come hidden danger to the colliery securing band.
In a word, existing chemical slip casting strengthening material because have that viscosity is high, the property annotated is poor, low strength, the not fire-retardant and defective such as be detrimental to health, can not satisfy the grouting and reinforcing requirement of fractured coal and rock in some situation, therefore, in the urgent need to low viscosity, high strength, the fire-retardant and slip casting strengthening material that is not detrimental to health.
Summary of the invention
The purpose of this invention is to provide a kind of bi-component flame-retardant low viscosity unsaturated polyester resin and preparation method thereof, make the resin for preparing can inject fragmentation, loose coal and rock, fast setting also provides good consolidation effect.
The objective of the invention is to be achieved through the following technical solutions.
The invention provides a kind of bi-component flame-retardant low viscosity unsaturated polyester resin, it prepares as follows:
1) dibasic alcohol and diprotic acid/acid anhydrides are heated to 160 ℃～170 ℃ and begin reaction, and be warming up to gradually 210 ℃～220 ℃, and under this temperature, carry out polycondensation;
2) reaction 8～12h (after preferred 9.5～10.5h), when the acid number of reactant reaches 60～80mgKOH/g (preferred 70～75), adds stopper;
When 3) reactant is cooled to 120～140 ℃ (preferred 130～135 ℃), reactant is added in the linking agent dilute, obtain the basestocks of unsaturated polyester resin after mixing;
4) in the amount of the basestocks 1/2 of the unsaturated polyester resin that obtains, add promotor and obtain the A component, in the amount of the basestocks of the unsaturated polyester resin that obtains other 1/2, add solidifying agent and obtain the B component.
Described dibasic alcohol is selected from a kind of, two or more combination in propylene glycol, ethylene glycol and the Diethylene Glycol, the combination of preferred ethylene glycol and propylene glycol, and wherein, the mol ratio of ethylene glycol and propylene glycol is preferably (0.5～1.5): 1.
Described diprotic acid/acid anhydrides comprises monounsaturated dicarboxylic acid/acid anhydrides and unsaturated dibasic acid/acid anhydrides (monounsaturated dicarboxylic acid/acid anhydrides and unsaturated dibasic acid/acid anhydrides must exist simultaneously); Wherein, the mol ratio of monounsaturated dicarboxylic acid/acid anhydrides and unsaturated dibasic acid/acid anhydrides is (0.6～1.2): 1, be preferably (0.8～1): 1.
Described monounsaturated dicarboxylic acid/acid anhydrides is selected from one or more combinations in phthalic acid, terephthalic acid, m-phthalic acid, Tetra hydro Phthalic anhydride and the tetrabromophthalic anhydride, and preferred Tetra hydro Phthalic anhydride and/or tetrabromo are for Tetra hydro Phthalic anhydride.
Described unsaturated dibasic acid/acid anhydrides is selected from MALEIC ANHYDRIDE or FUMARIC ACID TECH GRADE or two kinds of combinations, preferred MALEIC ANHYDRIDE.
Described diprotic acid/acid anhydrides also contains haloid element.
The mol ratio of described dibasic alcohol and diprotic acid/acid anhydrides is (1～1.15): 1, and preferred value is (1.07～1.1): 1.
Described stopper is Resorcinol, and the add-on of stopper is 0.01～0.04wt% of dibasic alcohol and diprotic acid/acid anhydrides throwing amount sum, and preferred value is 0.015～0.03wt%.
Described linking agent is the vinyl linking agent, namely contains single or two CH
2The polymerisable monomer of=C-group; The add-on of described linking agent is 70～90wt% of dibasic alcohol and diprotic acid/acid anhydrides throwing amount sum, and preferred value is 75～85wt%.
Described vinyl linking agent is vinylbenzene and Vinylstyrene; Wherein, the mol ratio of described vinylbenzene and Vinylstyrene is (7.5～9.5): 1, and preferred value is (8～9): 1.
Described step 1) in, when selecting halogenated acid/acid anhydrides as polymerization single polymerization monomer, also adds catalyzer in dibasic alcohol and the diprotic acid/acid anhydrides; Catalyzer is preferably trolamine, and the catalyzer add-on is 0.4～0.5wt% of dibasic alcohol and diprotic acid/acid anhydrides total amount.
Described step 3) in, also add fire retardant in the basestocks of unsaturated polyester resin, be preferably trichloroethyl phosphate, the add-on of fire retardant is 8～14wt% of gained unsaturated polyester resin basestocks total amount, and preferred value is 10～12wt%.(fire retardant is for select adding composition, if do not add, must resemble and adopt the polymerization single polymerization monomer that contains the halogen family element the embodiment 2, and for Tetra hydro Phthalic anhydride, otherwise material does not possess flame-retarding characteristic such as tetrabromo, and can not be called flame-retardant resin)
Described promotor is the carboxylate salt of transition metal, preferred cobalt iso-octoate, and the promotor add-on is 0.1～0.3wt% of A component total amount, preferred value is 0.15～0.25wt%.
Described solidifying agent is organo-peroxide, preferred methylethyl ketone peroxide, and the solidifying agent add-on is 0.2～0.6wt% of B component total amount, preferred value is 0.3～0.5wt%.
The basestocks of the unsaturated polyester resin that measuring process 3) prepares, its kinetic viscosity are 30～50mPas.With step 4) A component and 1: 1 by volume usefulness Double-liquid mud-injection pump of B component of obtaining be injected in the slit of fractured coal and rock, and its gel time is 10～40min, and be 20～60min set time.The ultimate compression strength of 24h was 45～65Mpa after this unsaturated polyester resin solidified, and had flame retardant resistance: the arithmetical av of spirit lamp test flaming combustion time is no more than 6s, and the arithmetical av of flameless combustion time is no more than 20s.
The present invention also provides the method for the above-mentioned bi-component flame-retardant low viscosity unsaturated polyester resin of preparation, and it prepares as follows:
1) dibasic alcohol and diprotic acid/acid anhydrides are heated to 160 ℃～170 ℃ and begin reaction, and be warming up to gradually 210 ℃～220 ℃, and under this temperature, carry out polycondensation;
2) reaction 8～12h (after preferred 9.5～10.5h), when the acid number of reactant reaches 60～80mgKOH/g (preferred 70～75), adds stopper;
When 3) reactant is cooled to 120～140 ℃ (preferred 130～135 ℃), reactant is added in the linking agent dilute, obtain the basestocks of unsaturated polyester resin after mixing;
4) in the amount of the basestocks 1/2 of the unsaturated polyester resin that obtains, add promotor and obtain the A component, in the amount of the basestocks of the unsaturated polyester resin that obtains other 1/2, add solidifying agent and obtain the B component.
Preparation method provided by the invention reaches the purpose that reduces resin viscosity by adding stopper control molecular weight and linking agent, thereby improve the intensity of cross-linking density and rigidity of material raising material by adding Vinylstyrene, reach the fire-retardant purpose of material by introducing flame retardant components, promotor and solidifying agent are added respectively unsaturated polyester resin formation A, B component, be injected into the stratum with grouting pump, form firm consolidation structure.
Beneficial effect of the present invention is: the product that the present invention prepares is a kind of low viscosity, high strength, set time is adjustable, the slip casting strengthening material that has flame-retarding characteristic and be not detrimental to health, after this material adopts the Double-liquid mud-injection pump of 1: 1 (volume ratio) to inject the breaking surrounding rock and loose coal rock mass of the underground workss such as colliery, can be penetrated at an easy rate in the minute fissure or open structure of coal and rock, after specific time solidifies, can be with loose, broken coal and rock is bonded to firm one-piece construction, play the effect of structural strengthening and reinforcement, thereby prevent roof fall, the generation of the disasters such as wall caving.
Embodiment
Following examples are used for explanation the present invention, but are not used for limiting the scope of the invention.
Embodiment 1
A kind of bi-component flame-retardant low viscosity unsaturated polyester resin, the polycondensation product for dibasic alcohol and diprotic acid or acid anhydrides prepares this unsaturated polyester resin, and the reaction raw materials that need to add and the quality of each raw material are as follows:
The preparation method is:
Ethylene glycol, propylene glycol, Tetra hydro Phthalic anhydride and MALEIC ANHYDRIDE are mixed, slowly be heated to 165 ℃ of beginning polycondensations (continuous warming process), and continue to be warming up to 215 ℃, and under this temperature, react when reaching 70mgKOH/g to acid number, add hydroquinone of polymerization retarder, rear cooling stirs, when treating that polycondensation product cools to 135 ℃, join in the vinyl linking agent (mixture of vinylbenzene and Vinylstyrene), then add trichloroethyl phosphate and mix, namely get the basestocks of unsaturated polyester resin.Measure the above-mentioned unsaturated polyester resin for preparing, its resin viscosity is 43mPas.
Get above resin 100g adding 0.2g cobalt iso-octoate and namely get the A component; Other gets the 100g resin and adds 0.4g methylethyl ketone peroxide composition B component, A, B component were mixed in 1: 1 by volume, at room temperature its gel time is 18min25s, be 26min set time, uniaxial compressive strength is 51MPa, the spirit lamp test flaming combustion time is lower than 6s, and the flameless combustion time is lower than 20s.
The low viscosity unsaturated polyester resin reinforcement material that this method is prepared has good consolidation effect with Double-liquid mud-injection pump injection colliery soft and broken surrounding rocks.
Embodiment 2
A kind of bi-component flame-retardant low viscosity unsaturated polyester resin, the polycondensation product for dibasic alcohol and diprotic acid or acid anhydrides prepares this unsaturated polyester resin, and the reaction raw materials that need to add and the quality of each raw material are as follows:
The preparation method is:
With propylene glycol, tetrabromo for the slowly heating of putting together of Tetra hydro Phthalic anhydride, Tetra hydro Phthalic anhydride and MALEIC ANHYDRIDE mixture and catalyzer trolamine, progressively be warming up to 220 ℃, and remain on to react under this temperature to acid number and reach 70mgKOH/g, add hydroquinone of polymerization retarder, rear cooling stirs, when treating that polycondensation product cools to 130～140 ℃, join in the vinyl linking agent (mixture of vinylbenzene and Vinylstyrene), stir and namely get the basestocks of unsaturated polyester resin.Measure the above-mentioned unsaturated polyester resin for preparing, its resin viscosity is 48mPas.
Get above resin 100g adding 0.2g cobalt iso-octoate and namely get the A component; Other gets the 100g resin, add the 0.4g methylethyl ketone peroxide and form the B component, A, B component were mixed in 1: 1 by volume, can be fixed well under the room temperature, (gel time is 28min, set time 40min, uniaxial compressive strength is 47MPa) the spirit lamp test is lower than 6s the flaming combustion time, the flameless combustion time is lower than 20s.
The low viscosity unsaturated polyester resin reinforcement material that this method is prepared has good consolidation effect with Double-liquid mud-injection pump injection colliery soft and broken surrounding rocks.
Embodiment 3
A kind of bi-component flame-retardant low viscosity unsaturated polyester resin, the polycondensation product for dibasic alcohol and diprotic acid or acid anhydrides prepares this unsaturated polyester resin, and the reaction raw materials that need to add and the quality of each raw material are as follows:
The preparation method is:
Ethylene glycol, propylene glycol, Diethylene Glycol, Tetra hydro Phthalic anhydride and MALEIC ANHYDRIDE are mixed, be heated to 210 ℃ and under this temperature, react 12h, when acid number reaches 60mgKOH/g, add hydroquinone of polymerization retarder, rear cooling stirs, when treating that polycondensation product cools to 120 ℃, join in the vinyl linking agent (mixture of vinylbenzene and Vinylstyrene), then add trichloroethyl phosphate, stir and namely get the basestocks of unsaturated polyester resin, measure the above-mentioned unsaturated polyester resin for preparing, its resin viscosity is 45mPas.Get above resin 100g adding 0.3g cobalt iso-octoate and namely get the A component; Other gets the 100g resin and adds 0.6g methylethyl ketone peroxide composition B component, A, B component were mixed in 1: 1 by volume, at room temperature its gel time is 13min, be 20min set time, uniaxial compressive strength is 40MPa, the spirit lamp test flaming combustion time is lower than 6s, and the flameless combustion time is lower than 20s.
Embodiment 4
A kind of bi-component flame-retardant low viscosity unsaturated polyester resin, the polycondensation product for dibasic alcohol and diprotic acid or acid anhydrides prepares this unsaturated polyester resin, and the reaction raw materials that need to add and the quality of each raw material are as follows:
The preparation method is:
Dibasic alcohol is mixed with diprotic acid/acid anhydrides and heat, under 220 ℃ of conditions, react 8h, reach the 80mgKOH/g stopped heating to acid number, add hydroquinone of polymerization retarder, rear cooling stirs, when treating that polycondensation product is cooled to 140 ℃, join in the vinyl linking agent (mixture of vinylbenzene and Vinylstyrene), then add trichloroethyl phosphate, stir and namely get the basestocks of unsaturated polyester resin, measure the above-mentioned unsaturated polyester resin for preparing, its resin viscosity is 39mPas.
Get above resin 100g adding 0.1g cobalt iso-octoate and namely get the A component; Other gets the 100g resin and adds 0.6g methylethyl ketone peroxide composition B component, A, B component were mixed in 1: 1 by volume, at room temperature its gel time is 20min, be 26min set time, uniaxial compressive strength is 36MPa, the spirit lamp test flaming combustion time is lower than 6s, and the flameless combustion time is lower than 20s.
Comparative Examples
The quality of reaction raw materials and each raw material is as follows in the prior art:
Its preparation method is:
Dibasic alcohol is mixed with diprotic acid/acid anhydrides and heat, under 220 ℃ of conditions, react 16h, reach the 40mgKOH/g stopped heating to acid number, add hydroquinone of polymerization retarder, the rear cooling that stirs adds copper naphthenate and TBC, when treating that polycondensation product is cooled to 120 ℃ in the vinylbenzene, join in the vinylbenzene that contains stopper, stirring namely gets unsaturated polyester resin.This unsaturated polyester resin is not had a flame retardant resistance, and resin viscosity can't inject the stratum more than 200mPas, can not be used as to reinforce ravelly ground.And embodiment 1～4 prepared two-pack flame retardant resistance low viscosity unsaturated polyester resin viscosity is low, and is fire-retardant, suits to do broken bottom reinforcement material and use.
Claims (10)
1. bi-component flame-retardant low viscosity unsaturated polyester resin, it prepares as follows:
1) dibasic alcohol and diprotic acid/acid anhydrides are heated to 160 ℃～170 ℃ and begin reaction, and be warming up to gradually 210 ℃～220 ℃, and under this temperature, carry out polycondensation;
2) reaction 8～12h when the acid number of reactant reaches 60～80mgKOH/g, adds stopper;
When 3) reactant is cooled to 120～140 ℃, reactant is added in the linking agent dilute, obtain the basestocks of unsaturated polyester resin after mixing; In the basestocks of unsaturated polyester resin, add fire retardant;
4) in the amount of the basestocks 1/2 of the unsaturated polyester resin that obtains, add promotor and obtain the A component, in the amount of the basestocks of the unsaturated polyester resin that obtains other 1/2, add solidifying agent and obtain the B component;
Wherein, described linking agent is vinylbenzene and Vinylstyrene, and its add-on is 70～90wt% of dibasic alcohol and diprotic acid/acid anhydrides throwing amount sum, and the mol ratio of described vinylbenzene and Vinylstyrene is (7.5～9.5): 1;
Described dibasic alcohol is selected from one or more in propylene glycol, ethylene glycol and the Diethylene Glycol; Described diprotic acid/acid anhydrides comprises monounsaturated dicarboxylic acid/acid anhydrides and unsaturated dibasic acid/acid anhydrides; The mol ratio of described monounsaturated dicarboxylic acid/acid anhydrides and unsaturated dibasic acid/acid anhydrides is 0.6～1.2:1, and described diprotic acid/acid anhydrides also contains haloid element; The mol ratio of described dibasic alcohol and diprotic acid/acid anhydrides is 1～1.15:1;
Described stopper is Resorcinol; 0.01～0.04wt% of the throwing amount sum that described stopper add-on is dibasic alcohol and diprotic acid/acid anhydrides;
8～14wt% of the basestocks total amount that described fire retardant add-on is the gained unsaturated polyester resin;
Described promotor is the carboxylate salt of transition metal; Described promotor add-on is 0.1～0.3wt% of A component total amount;
Described solidifying agent is organo-peroxide; Described solidifying agent add-on is 0.2～0.6wt% of B component total amount.
2. vibrin according to claim 1, it is characterized in that: the mol ratio of described monounsaturated dicarboxylic acid/acid anhydrides and unsaturated dibasic acid/acid anhydrides is 0.8～1:1; Described diprotic acid/acid anhydrides also contains haloid element.
3. vibrin according to claim 1, it is characterized in that: the mol ratio of described dibasic alcohol and diprotic acid/acid anhydrides is 1.07～1.1:1.
4. vibrin according to claim 1 is characterized in that: 0.015～0.03wt% of the throwing amount sum that described stopper add-on is dibasic alcohol and diprotic acid/acid anhydrides.
5. vibrin according to claim 1, the add-on that it is characterized in that described linking agent is 75～85wt% of the throwing amount sum of dibasic alcohol and diprotic acid/acid anhydrides.
6. vibrin according to claim 1 is characterized in that: in the described step 1), when described diprotic acid/acid anhydrides is halogenated acid/acid anhydrides, also add catalyzer in the polycondensation process; Described catalyzer add-on is 0.4～0.5wt% of dibasic alcohol and diprotic acid/acid anhydrides total amount.
7. vibrin according to claim 1 is characterized in that: 10～12wt% of the basestocks total amount that described fire retardant add-on is the gained unsaturated polyester resin.
8. vibrin according to claim 1, it is characterized in that: described promotor add-on is 0.15～0.25wt% of A component total amount.
9. vibrin according to claim 1, it is characterized in that: described solidifying agent add-on is 0.3～0.5wt% of B component total amount.
10. a method for preparing the bi-component flame-retardant low viscosity unsaturated polyester resin comprises the steps:
1) dibasic alcohol and diprotic acid/acid anhydrides are heated to 160 ℃～170 ℃ and begin reaction, and be warming up to gradually 210 ℃～220 ℃, and under this temperature, carry out polycondensation;
2) reaction 8～12h when the acid number of reactant reaches 60～80mgKOH/g, adds stopper;
When 3) reactant is cooled to 120～140 ℃, reactant is added in the linking agent dilute, obtain the basestocks of unsaturated polyester resin after mixing;
4) in the amount of the basestocks 1/2 of the unsaturated polyester resin that obtains, add promotor and obtain the A component, in the amount of the basestocks of the unsaturated polyester resin that obtains other 1/2, add solidifying agent and obtain the B component;
Wherein, described linking agent is vinylbenzene and Vinylstyrene, and its add-on is 70～90wt% of dibasic alcohol and diprotic acid/acid anhydrides throwing amount sum, and the mol ratio of described vinylbenzene and Vinylstyrene is (7.5～9.5): 1;
Described dibasic alcohol is selected from one or more in propylene glycol, ethylene glycol and the Diethylene Glycol; Described diprotic acid/acid anhydrides comprises monounsaturated dicarboxylic acid/acid anhydrides and unsaturated dibasic acid/acid anhydrides; The mol ratio of described monounsaturated dicarboxylic acid/acid anhydrides and unsaturated dibasic acid/acid anhydrides is 0.6～1.2:1, and described diprotic acid/acid anhydrides also contains haloid element; The mol ratio of described dibasic alcohol and diprotic acid/acid anhydrides is 1～1.15:1;
Described stopper is Resorcinol; 0.01～0.04wt% of the throwing amount sum that described stopper add-on is dibasic alcohol and diprotic acid/acid anhydrides; 8～14wt% of the basestocks total amount that described fire retardant add-on is the gained unsaturated polyester resin;
Described promotor is the carboxylate salt of transition metal; Described promotor add-on is 0.1～0.3wt% of A component total amount;
Described solidifying agent is organo-peroxide; Described solidifying agent add-on is 0.2～0.6wt% of B component total amount.
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| CN104693378A (en) * | 2015-03-24 | 2015-06-10 | 上海米维矿业科技有限公司 | Rapid concretion seriflux injecting material for coal mine laneway water flow sand layer and preparing method thereof |
| CN105062333A (en) * | 2015-08-26 | 2015-11-18 | 成都展辰涂料有限公司 | Glossy unsaturated polyester finish paint |
| CN106366251A (en) * | 2016-08-27 | 2017-02-01 | 安徽省新力复合材料有限公司 | Antibacterial low-viscosity unsaturated polyester resin for anchoring agent |
| CN106366250A (en) * | 2016-08-27 | 2017-02-01 | 安徽省新力复合材料有限公司 | Anti-corrosion unsaturated polyester resin for anchoring agent and preparation method thereof |
| CN106366542A (en) * | 2016-08-27 | 2017-02-01 | 安徽省新力复合材料有限公司 | Antibacterial aging resistant unsaturated polyester resin |
| CN106280196A (en) * | 2016-08-27 | 2017-01-04 | 安徽省新力复合材料有限公司 | A kind of heat resistant unsaturated polyester resin |
| CN106589250A (en) * | 2016-12-03 | 2017-04-26 | 安徽富丽华化工有限公司 | High hardness and toughness modified unsaturated polyester resin and preparation method thereof |
| CN111333876A (en) * | 2020-01-06 | 2020-06-26 | 泰州市中盛机电有限公司 | Resin mixing method |
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| CN101225215A (en) * | 2007-12-05 | 2008-07-23 | 青岛科技大学 | Hydrogel-containing unsaturated polyester resin flame-retardant composite material and preparation method thereof |
| CN101514253A (en) * | 2008-12-31 | 2009-08-26 | 上海新天和树脂有限公司 | Environment-friendly flame-retarded unsaturated polyester resin and preparation method thereof |
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| CN101225215A (en) * | 2007-12-05 | 2008-07-23 | 青岛科技大学 | Hydrogel-containing unsaturated polyester resin flame-retardant composite material and preparation method thereof |
| CN101514253A (en) * | 2008-12-31 | 2009-08-26 | 上海新天和树脂有限公司 | Environment-friendly flame-retarded unsaturated polyester resin and preparation method thereof |
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