CN105622858A - Environment-friendly styrene-free unsaturated polyester resin synthesis method - Google Patents
Environment-friendly styrene-free unsaturated polyester resin synthesis method Download PDFInfo
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- CN105622858A CN105622858A CN201511014282.1A CN201511014282A CN105622858A CN 105622858 A CN105622858 A CN 105622858A CN 201511014282 A CN201511014282 A CN 201511014282A CN 105622858 A CN105622858 A CN 105622858A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/68—Unsaturated polyesters
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/68—Unsaturated polyesters
- C08G18/683—Unsaturated polyesters containing cyclic groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—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
- C08G63/54—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation the acids or hydroxy compounds containing carbocyclic rings
-
- 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
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/676—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
Abstract
The invention relates to an environment-friendly unsaturated polyester resin synthesis method, aims at solving the technical problem of exhaust of harmful gas of styrene in ordinary products, and belongs to the technical field of unsaturated polyester resin synthesis. The synthesis method is characterized in that saturated binary acid, unsaturated binary acid and dihydric alcohol which has the total mass percentage being 25 percent to 55 percent are sequentially fed into a reaction container; nitrogen gas is introduced, and temperature rise is performed, so that polymerization reaction is performed, and double-end hydroxyl unsaturated polyester is obtained; according to the hydroxyl molar weight n of the obtained product, isocyanate is added into an acrylic crosslinking monomer; then, the double-end hydroxyl unsaturated polyester is added, so that the isocyanate and the double-end hydroxyl unsaturated polyester are subjected to copolymerization, and a segmented copolymer with -NCO groups at two ends is obtained; the molar weight N of the -NCO of the segmented copolymer is determined; 1.03N mole of hydroxyl acrylate is slowly dripped. The synthesis method has the advantages that the resin product does not contain the styrene, so that the requirement of environment protection is achieved, and the body health of workers is protected.
Description
Technical field
The present invention relates to the synthetic method of a kind of environment-friendly unsaturated polyester resin, particularly relate to a kind of by the synthesis technique of hydroxy acrylate and isocyanate block copolymerization modified unsaturated polyester resin, belong to process for synthesizing unsaturated polyester resin technical field.
Background technology
Vinylbenzene plays dual parts thinner and linking agent in unsaturated polyester resin. It is cheap, and has higher reactive behavior between unsaturated polyester, and is the good solvent of multiple vibrin. So, vinylbenzene is still the reactive monomer that in process for synthesizing unsaturated polyester resin, consumption is maximum at present, usually accounts for resin quality 30%-50%. But, the normal temperature vapour pressure of vinylbenzene is 0.7kPa(20 DEG C), boiling point 145 DEG C, easily volatilization, in glass reinforced plastic moulding process, especially in the die sinking moulding processs such as injection, heavy caliber winding and hand paste, a large amount of volatilization, causing production plant smell big, environmental pollution is serious, and harm workman is healthy. The maximum mean concns of vinylbenzene in the 8h of working space: reach 420mg/m before China3, oneself is through there being very big progress now, controls at 210mg/m3, but still have many gaps compared with advanced country in the world, such as Britain 100mg/m3, U.S. 50mg/m3, Germany only 20mg/m3Etc.. Along with being rooted in the hearts of the people of environmental protection concept, relevant departments of China and the public also start to pay close attention to the harm of vinylbenzene, effectively suppress the styrene gas content in vinylbenzene volatilization, limit production workshop, and research and development resins with low styrene emission resin has become the striving direction of current glass reinforced plastic industry. Existing document report, as the name of Changzhou China Tech resin company limited " resins with low styrene emission unsaturated polyester gel coating resin and its preparation method " (application publication number CN102627740A), the research and development of China Resources, Changzhou resin composite materials company limited be called " a kind of vinylbenzene volatilization inhibitor and the unsaturated polyester containing it " (CN103408792A) and industrial chemical research institute of Poland " ... manufacture the method with the unsaturated polyester resin suppressing monomer component volatile nature " (publication number CN1113657A) etc.
On market, resins with low styrene emission resin mainly contains three classes: 1) add the membrane-forming agent suppressing vinylbenzene volatilization, such as paraffin etc.; 2) unsaturated polyester resin of low-styrene-content is synthesized, such as DCPD modified resin; 3) monomer that employing volatility is low is such as substituted phenylethylenes such as Vinyl toluenes. Its shortcoming is: uses the film for additive suppressing vinylbenzene volatilization, can only reduce the volatilization of vinylbenzene on a small quantity, the volatile quantity of vinylbenzene generally can only be made to reduce by 30%, can't reach the requirement of environmental protection resins with low styrene emission.
Summary of the invention
The present invention seeks to fundamentally to solve the volatilization problem of vinylbenzene, there is provided a kind of environment-friendly type without the synthetic method of vinylbenzene unsaturated polyester resin, utilize the esters of acrylic acid substituted phenylethylene of not easily volatilization, colorless and odorless or colourless low smell, copolymerzation with cross-linking is carried out with the unsaturated polyester resin of crylic acid hydroxy ester and isocyanate block copolymerization modification, thus thoroughly eliminate vinylbenzene, reach the requirement of environmental protection.
For achieving the above object, the technical scheme of employing is, a kind of environment-friendly type is without the synthetic method of vinylbenzene unsaturated polyester resin, it is characterised in that: comprise the steps: successively
(1) get the raw materials ready: setting the finished product environment-friendly type without the mass percent of vinylbenzene unsaturated polyester resin as 100%, the mass percent shared by each component is:
Monounsaturated dicarboxylic acid 6��35%
Unsaturated dibasic acid 1.8��20%
Dibasic alcohol 10��32%
Isocyanic ester 8��25%
Catalyzer 0.2��1.0%
Hydroxy acrylate 7��18%
Stopper 0.01��0.1%
Crosslinkable monomers 30��45%
(2) it is polymerized: stir in four mouthfuls of reaction vessels with condensation at band, dropping into total mass number successively is the monounsaturated dicarboxylic acid of 25%��55%, unsaturated dibasic acid and dibasic alcohol, logical nitrogen also stirs, slowly it is warming up to l60 DEG C, maintain after 1 hour and to heat up gradually again and holding temperature l90��2l0 DEG C makes its polymerization reaction take place, control head temperature is lower than 105 DEG C, until acid number is close or reaches 60mgKOH/g, stop logical nitrogen, start to vacuumize, temperature remains within 200 DEG C, until polymkeric substance acid number is less than 10mgKOH/g in reaction vessel, and aquifer yield constant time be reaction end, then it is cooled to the stopper that l80 DEG C adds 0.005��0.05%, continues stirring and be cooled to room temperature, obtain two hydroxyl terminated unsaturated polyester that mean polymerisation degree is 1��6,
(3) copolymerization: it is n that the hydroxyl value of the two hydroxyl terminated unsaturated polyester obtained according to described step (1) calculates the molar weight of hydroxyl, the isocyanic ester getting n mole joins in the acrylic acid or the like cross-linking monomer that total mass number is 30%��45%, and then under the temperature agitation condition of 60��70 DEG C, progressively add described pair of hydroxyl terminated unsaturated polyester, and slowly heat up and make described isocyanic ester and described pair of hydroxyl terminated unsaturated polyester carry out copolyreaction, reaction process measured a hydroxyl value and isocyano-content (-NCO) every 1 hour, react after 3��4 hours, when hydroxyl value is less than 15mgKOH/g, when isocyano-content (-NCO) is reduced to below 2% simultaneously, add 0.1��0.5% catalyzer, react 1 hour again, it it is reaction end when hydroxyl value is less than 5mgKOH/g, obtain the segmented copolymer that two ends are all isocyano (-NCO) groups,
(4) end-blocking: measure the molar weight N of NCO that the two ends that described step (3) synthesizes are all the segmented copolymers of isocyano (-NCO) group, first add 0.1��0.5% catalyzer, then the hydroxy acrylate adding 1.03N mole is slowly dripped, after described hydroxy acrylate dropwises, more slowly it is warming up to 60��75 DEG C, continues reaction 3��5 hours, measure its hydroxyl value and isocyano-content again, when hydroxyl value is less than 5mgKOH/g, when isocyano-content is 0, it it is reaction end; Adding 0.005��0.05% stopper and be stirred to room temperature, so far environment-friendly type is complete without the synthesis of vinylbenzene unsaturated polyester resin.
Described monounsaturated dicarboxylic acid refers to one or both in Tetra hydro Phthalic anhydride, m-phthalic acid, terephthalic acid, hexanodioic acid.
Described unsaturated dibasic acid refers to one or more in maleic acid (toxilic acid), MALEIC ANHYDRIDE (maleic anhydride is called for short along acid anhydride), FUMARIC ACID TECH GRADE (fumaric acid).
Described dibasic alcohol refers to one or more in ethylene glycol, propylene glycol, glycol ether, dipropylene glycol, neopentyl glycol, dibromoneopentyl glycol, butyleneglycol, hexylene glycol, bisphenol-a derivative, Hydrogenated Bisphenol A, vinyl carbinol.
Described hydroxy acrylate is the one in methacrylic acid hydroxyl second ester (HEMA write a Chinese character in simplified form in English) and methacrylic acid hydroxyl propyl ester (HPMA write a Chinese character in simplified form in English).
Described isocyanic ester comprises one or more in tolylene diisocyanate (TDI write a Chinese character in simplified form in English), diphenylmethanediisocyanate (MDI write a Chinese character in simplified form in English), hexamethylene diisocyanate (HDI write a Chinese character in simplified form in English), PPDI, 1,4-cyclohexyl diisocyanate.
Described esters of acrylic acid cross-linking monomer refers to one or more in hexanediyl ester (HDDA), two diacrylates of Poly-propylene glycols (DPGDA), tripropylene glycol diacrylate (TPGDA), Viscoat 295 (TMPTA), tetramethylol methane tetraacrylate (PETTA).
Described catalyzer is one or both in tetramethyl-butylamine, triethylene diamine, two lauric acid dibutene base tin, stannous octoate.
Described stopper is one or both in methyl-phenoxide, Resorcinol, methyl hydroquinone, para benzoquinone, p-ten.-butylcatechol, Tert. Butyl Hydroquinone.
Environment-friendly unsaturated polyester resin synthesized by the present invention is compared with common resins with low styrene emission unsaturated polyester resin with general unsaturated polyester resin, has the following advantages:
(1) no longer containing vinylbenzene in resin; and employ the esters of acrylic acid thinner of difficult volatilization; produce the unsaturated polyester resin of tasteless or low smell; reach the requirement of environmental protection, also effectively improve the operating environment of glass reinforced plastic manufacturing concern production scene, protect the health of human body of workman.
(2) chemical structure with the alternately block copolymerization of regular isocyanate groups and unsaturated polyester group, macromolecular main chain not only has polar group, and molecular weight and unit structure can carry out molecular designing and adjustment according to shaping needs. Viscosity during machine-shaping, gel time and final curing time etc. are all more easy to control and measure.
(3) by hydroxy acrylate and isocyanic ester to the block polymerization modification of unsaturated polyester, unsaturated molecular chain introduces the double bond in acrylate and carbamate groups, the former can carry out good copolymerization with the monomer diluent of esters of acrylic acid, improves the shortcoming of the solidification bad (copolymerization is bad) between double bond and acrylic ester monomer thinner introduced merely by unsaturated dibasic acid in unsaturated polyester; The latter carbamate groups system is introduced by isocyanic ester and hydroxyl terminated unsaturated polyester copolyreaction, improve the polarity of molecule, improve the mechanical property of matrix resin on the one hand, significantly improve again the adhesive property of matrix resin and glass fibre on the other hand; And storage environment and solidifying requirements are equal to general unsaturated polyester resin completely.
Embodiment
By embodiment, the present invention is described more in detail as follows. Embodiment comprises the steps successively, it relates to each constituent mass percentage ratio, as without indicating especially, all taking the mass percent of the finished product as 100% calculating.
Embodiment 1:
Step (1) is aggregated in four mouthfuls of flasks to drop into 444g Tetra hydro Phthalic anhydride, 49g MALEIC ANHYDRIDE and 495g glycol ether successively, logical nitrogen also heats, open and stir, be slowly warming up to l60 DEG C, maintain this temperature and be warming up to l90��2l0 DEG C gradually again after 1 hour, control evaporates a temperature lower than 105 DEG C, until acid number reaches or close to about 60mgKOH/g, stops logical nitrogen, starts to vacuumize, temperature remains within 200 DEG C, until being reaction end when acid number is less than 10mgKOH/g. Be cooled to the hydroquinone of polymerization retarder discharging that 8O DEG C adds 0.16g, predetermined mean polymerisation degree be 3 two hydroxyl terminated unsaturated polyester.
Step (2) copolymerization adds 800gTPGDA in new there-necked flask, 580.4gMDI, then 60 DEG C under agitation it are warming up to, then divide and add two hydroxyl terminated unsaturated polyester for 3��4 times, control temperature of reaction is at 60��70 DEG C, reaction process measured a hydroxyl value and isocyano-content (-NCO) every 1 hour, when hydroxyl value is less than 15mgKOH/g, when simultaneously-NCO content reaches below 2%, add catalyzer 2.2g bis-lauric acid dibutene base tin, it it is reaction end when hydroxyl value is less than 5mgKOH/g, two ends are all the segmented copolymers of isocyano (-NCO) group.
Step (3) end-blocking measures the isocyano-content (-NCO) of the unsaturated polyester resin of the isocyanate block copolymerization modification that described step (2) is synthesized, and slowly drips the HPMA adding 334.7g in flask. After dropwising, then keep temperature to 60��75 DEG C of reaction system, continue reaction 3��5 hours, then measure its hydroxyl value and isocyano-content, when hydroxyl value is less than 5mgKOH/g, when isocyano-content is 0, be reaction end. Adding the stopper methyl-phenoxide of 0.18g and be stirred to room temperature, so far environment-friendly type is complete without the announcement synthesis of vinylbenzene unsaturated polyester resin.
Embodiment 2:
By m-phthalic acid 664g, maleic acid 116.07g, propylene glycol 456.54g drops in the device shown in embodiment 1, in subsequent step, crosslinkable monomers changes the HDDA adding 820g into, isocyanic ester in copolymerization step changes into the TDI of 312g, and catalyzer changes into and adds two lauric acid dibutene base tin 2.1g, changes the HPMA in step (3) into 252g, stopper changes into and adds 0.2g methyl hydroquinone and 0.1g Tert. Butyl Hydroquinone, and all the other are by step operation similarly to Example 1.
Embodiment 3:
By hexanodioic acid 292.3g, FUMARIC ACID TECH GRADE 116.07g, propylene glycol 198g, glycol ether 106g drops in the device shown in embodiment 1, stopper in the first step is changed into 0.08g Resorcinol and 0.09g p-ten.-butylcatechol, crosslinkable monomers is changed into the TMPTA of HDDA and 182g adding 600g by subsequent step, the isocyanic ester of copolymerization end-blocking is changed into the MDI of 274g, catalyzer changes into and adds 2.4g triethylene diamine, change the hydroxy acrylate of end-blocking in step (3) HEMA of 148g into, stopper changes into and adds 0.14g methyl hydroquinone and 0.08g Tert. Butyl Hydroquinone, all the other are by step operation similarly to Example 1.
Embodiment 4:
By Tetra hydro Phthalic anhydride 222g, MALEIC ANHYDRIDE 147g, propylene glycol 190g, glycol ether 106g drops in the device shown in embodiment 1, in subsequent step, crosslinkable monomers changes the DPGDA of HDDA and 168g adding 600g into, the isocyanic ester of copolymerization end-blocking is changed into the TDI of 160g, catalyzer changes into and adds 2.6g triethylene diamine, and change the hydroxy acrylate of end-blocking in step (3) HEMA of 130g into, stopper changes into and adds 0.13g methyl-phenoxide and 0.07g p-ten.-butylcatechol, and all the other are by step operation similarly to Example 1.
Embodiment 5:
By terephthalic acid 166g, MALEIC ANHYDRIDE 196g, propylene glycol 205g, glycol ether 106g, ethylene glycol 19g drops in the device shown in embodiment 1, in subsequent step, crosslinkable monomers changes the TPGDA of HDDA and 170g adding 650g into, the isocyanic ester of copolymerization end-blocking is changed into the TDI of 328g, catalyzer changes into and adds 2.6g triethylene diamine, and change the hydroxy acrylate of end-blocking in step (3) HPMA of 270g into, stopper changes into and adds 0.18g methyl-phenoxide and 0.07g para benzoquinone, and all the other are by step operation similarly to Example 1.
Embodiment 6:
By Tetra hydro Phthalic anhydride 592g, MALEIC ANHYDRIDE 98g, glycol ether 583.6g, Hydrogenated Bisphenol A 120.2g drops in the device shown in embodiment 1, in subsequent step, crosslinkable monomers changes the HDDA adding 1200g into, the isocyanic ester of copolymerization end-blocking is changed into the TDI of 320g, catalyzer changes into and adds 2.8g bis-lauric acid dibutene base tin, and change the hydroxy acrylate of end-blocking in step (3) HEMA of 243g into, stopper changes into and adds 0.2g methyl-phenoxide and 0.05g para benzoquinone, and all the other are by step operation similarly to Example 1.
Embodiment 7:
By Tetra hydro Phthalic anhydride 296g, MALEIC ANHYDRIDE 98g, propylene glycol 190g, glycol ether 133g drops in the device shown in embodiment 1, crosslinkable monomers is changed into HDDA and 60gTMPTA adding 640g by subsequent step, the isocyanic ester of copolymerization end-blocking is changed into the HDI of 230g, catalyzer changes into and adds 2.2g bis-lauric acid dibutene base tin, and change the hydroxy acrylate of end-blocking in step (3) HPMA of 202g into, stopper changes into and adds 0.15g methyl-phenoxide and 0.05g Resorcinol, and all the other are by step operation similarly to Example 1.
Embodiment 8:
By Tetra hydro Phthalic anhydride 148g, MALEIC ANHYDRIDE 196g, propylene glycol 190g, glycol ether 159g drops in the device shown in embodiment 1, crosslinkable monomers is changed into HDDA and 60gTMPTA adding 680g by subsequent step, the isocyanic ester of copolymerization end-blocking is changed into the HDI of 300g, catalyzer changes into and adds 1.5g stannous octoate and 1.5g triethylene diamine, and change the hydroxy acrylate of end-blocking in step (3) HPMA of 265g into, stopper changes into and adds 0.18g methyl-phenoxide, and all the other are by step operation similarly to Example 1.
Embodiment 9:
By m-phthalic acid 166g, MALEIC ANHYDRIDE 98g, propylene glycol 190g, glycol ether 106g, ethylene glycol 15.52g drops in the device shown in embodiment 1, in subsequent step, crosslinkable monomers changes HDDA and 60gTMPTA adding 600g into, the isocyanic ester of copolymerization end-blocking is changed into the TDI of 340g, catalyzer changes into and adds 3g triethylene diamine, and change the hydroxy acrylate of end-blocking in step (3) HEMA of 265g into, stopper changes into and adds 0.15g methyl-phenoxide, and all the other are by step operation similarly to Example 1.
Embodiment 10
By Tetra hydro Phthalic anhydride 296g, MALEIC ANHYDRIDE 98g, propylene glycol 228.3g, dipropylene glycol 134g drops in the device shown in embodiment 1, in subsequent step, crosslinkable monomers changes into and adds 1000gHDDA and 100gTPGDA, the isocyanic ester of copolymerization end-blocking is changed into the MDI of 470g, catalyzer changes into and adds two lauric acid dibutene base tin 2.9g, and change the hydroxy acrylate of end-blocking in step (3) HEMA of 260g into, stopper changes into and adds 0.15g para benzoquinone, and all the other are by step operation similarly to Example 1.
Embodiment 11
By adipic acid 73g, m-phthalic acid 83.5g, FUMARIC ACID TECH GRADE 232g, propylene glycol 228g, neopentyl glycol 104g drops in the device shown in embodiment 1, in subsequent step, crosslinkable monomers changes into and adds 800gHDDA and 100gTPGDA and 40gPETTA, the isocyanic ester of copolymerization end-blocking is changed into the MDI of 480g, catalyzer changes into and adds two lauric acid dibutene base tin 2.2g, and change the hydroxy acrylate of end-blocking in step (3) HEMA of 260g into, stopper changes into and adds 0.2g methyl hydroquinone and 0.1g Tert. Butyl Hydroquinone, all the other are by step operation similarly to Example 1.
Embodiment 12
By adipic acid 73g, terephthalic acid 83.5g, FUMARIC ACID TECH GRADE 232g, propylene glycol 38g, dipropylene glycol 368.5g, ethylene glycol 31g drops in the device shown in embodiment 1, crosslinkable monomers is changed into by subsequent step and adds 800gHDDA and 50gTPGDA and 30gPETTA, the isocyanic ester of copolymerization is changed into the MDI of 360g, catalyzer changes into and adds dibutyl tin laurate 2.2g, and changing the hydroxy acrylate of end-blocking in step (3) HPMA of 210g into, stopper changes into and adds 0.2g methyl-phenoxide, and all the other are by step operation similarly to Example 1.
Embodiment 13
By hexanodioic acid 194.2g, MALEIC ANHYDRIDE 65.7g, propylene glycol 182.6g, neopentyl glycol 62.5g drops in the device shown in embodiment 1, in subsequent step, crosslinkable monomers changes into and adds 560gHDDA and 80gTPGDA and 40gPETTA, the isocyanic ester of copolymerization end-blocking changes into 320gTDI catalyzer change into and add 2.2g bis-lauric acid dibutene base tin, and change the hydroxy acrylate of end-blocking in step (3) HPMA of 270 into, stopper changes into and adds 0.24g methyl-phenoxide, and all the other are by step operation similarly to Example 1.
In each embodiment, the typical quality index of gained resin is as follows above:
| Project | Technical indicator | Testing method |
| Outward appearance | Light color clear viscous liquids | Range estimation |
| Acid number, mgKOH/g | 10��25 | GB/T2895-1987 |
| Viscosity (25 DEG C), Pa s | 0.25��0.55 | GB/T7193.1-1987 |
| Solids content, % | 55��70 | GB/T7193.3-1987 |
| Gel time (25 DEG C), min | 15��35 | GB/T7193.6-1987 5 --> |
| Exothermic peak, DEG C | 130��190 | 25 DEG C, 100g resin |
The typical mechanical property of casting resin is as follows:
| Project | Technical indicator | Testing method |
| Ba Keer hardness | 45��55 | GB/T 3854-2005 |
| Tensile strength, MPa | 60��75 | GB/T 2567-2008 |
| Tensile modulus, MPa | 3500��3600 | GB/T 2567-2008 |
| Elongation at break, % | 2��3 | GB/T 2567-2008 |
| Flexural strength, MPa | 115��135 | GB/T 2567-2008 |
| Modulus in flexure, MPa | 3700��3900 | GB/T 2567-2008 |
| Heat-drawn wire (1.8MPa), DEG C | 80��90 | GB/T 1634-2004 |
| Indoor vinylbenzene mean concns in 8 hours | �Q210mg/m3 | 20kg resin is uncovered to be placed in 20 square meter rooms |
Claims (7)
1. an environment-friendly type is without the synthetic method of vinylbenzene unsaturated polyester resin, it is characterised in that: comprise the steps: successively
(1) get the raw materials ready: setting the finished product environment-friendly type without the mass percent of vinylbenzene unsaturated polyester resin as 100%, the mass percent shared by each component is:
Monounsaturated dicarboxylic acid 6��35%
Unsaturated dibasic acid 1.8��20%
Dibasic alcohol 10��32%
Isocyanic ester 8��25%
Catalyzer 0.2��1.0%
Hydroxy acrylate 7��18%
Stopper 0.01��0.1%
Crosslinkable monomers 30��45%
(2) it is polymerized: stir in four mouthfuls of reaction vessels with condensation at band, dropping into total mass number successively is the monounsaturated dicarboxylic acid of 25%��55%, unsaturated dibasic acid and dibasic alcohol, logical nitrogen also stirs, slowly it is warming up to l60 DEG C, maintain after 1 hour and to heat up gradually again and holding temperature l90��2l0 DEG C makes its polymerization reaction take place, control head temperature is lower than 105 DEG C, until acid number is close or reaches 60mgKOH/g, stop logical nitrogen, start to vacuumize, temperature remains within 200 DEG C, until polymkeric substance acid number is less than 10mgKOH/g in reaction vessel, and aquifer yield constant time be reaction end, then it is cooled to the stopper that l80 DEG C adds 0.005��0.05%, continues stirring and be cooled to room temperature, obtain two hydroxyl terminated unsaturated polyester that mean polymerisation degree is 1��6,
(3) copolymerization: it is n that the hydroxyl value of the two hydroxyl terminated unsaturated polyester obtained according to described step (1) calculates the molar weight of hydroxyl, the isocyanic ester getting n mole joins in the acrylic acid or the like cross-linking monomer that total mass number is 30%��45%, and then under the temperature agitation condition of 60��70 DEG C, progressively add described pair of hydroxyl terminated unsaturated polyester, and slowly heat up and make described isocyanic ester and described pair of hydroxyl terminated unsaturated polyester carry out copolyreaction, reaction process measured a hydroxyl value and isocyano-content (-NCO) every 1 hour, react after 3��4 hours, when hydroxyl value is less than 15mgKOH/g, when isocyano-content (-NCO) is reduced to below 2% simultaneously, add 0.1��0.5% catalyzer, react 1 hour again, it it is reaction end when hydroxyl value is less than 5mgKOH/g, obtain the segmented copolymer that two ends are all isocyano (-NCO) groups,
(4) end-blocking: measure the NCO molar weight N that the two ends that described step (3) synthesizes are all the segmented copolymers of isocyano (-NCO) group, first add 0.1��0.5% catalyzer, then the hydroxy acrylate adding 1.03N mole is slowly dripped, after described hydroxy acrylate dropwises, slowly it is warming up to 60��75 DEG C again, continues reaction 3��5 hours, then measure its hydroxyl value and isocyano-content, when hydroxyl value is less than 5mgKOH/g, it is reaction end when isocyano-content is 0; Adding 0.005��0.05% stopper and be stirred to room temperature, so far environment-friendly type is complete without the synthesis of vinylbenzene unsaturated polyester resin.
2. press a kind of environment-friendly type described in claim 1 without the synthetic method of vinylbenzene unsaturated polyester resin, it is characterised in that: described monounsaturated dicarboxylic acid refers to one or both in Tetra hydro Phthalic anhydride, m-phthalic acid, terephthalic acid, hexanodioic acid.
3. press a kind of environment-friendly type described in claim 1 without the synthetic method of vinylbenzene unsaturated polyester resin, it is characterized in that: described unsaturated dibasic acid refers to one or more in maleic acid (toxilic acid), MALEIC ANHYDRIDE (maleic anhydride is called for short along acid anhydride), FUMARIC ACID TECH GRADE (fumaric acid).
4. press a kind of environment-friendly type described in claim 1 without the synthetic method of vinylbenzene unsaturated polyester resin, it is characterised in that: described dibasic alcohol refers to one or more in ethylene glycol, propylene glycol, glycol ether, dipropylene glycol, neopentyl glycol, dibromoneopentyl glycol, butyleneglycol, hexylene glycol, bisphenol-a derivative, Hydrogenated Bisphenol A, vinyl carbinol.
5. by the synthetic method of a kind of environment-friendly type described in claim 1 without vinylbenzene unsaturated polyester resin, it is characterised in that: described hydroxy acrylate is the one in methacrylic acid hydroxyl second ester and methacrylic acid hydroxyl propyl ester.
6. press a kind of environment-friendly type described in claim 1 without the synthetic method of vinylbenzene unsaturated polyester resin, it is characterized in that: described isocyanic ester comprises one or more in tolylene diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate, PPDI, 1,4-cyclohexyl diisocyanate.
7. press a kind of environment-friendly type described in claim 1 without the synthetic method of vinylbenzene unsaturated polyester resin, it is characterised in that: described esters of acrylic acid cross-linking monomer refers to one or more in hexanediyl ester, two diacrylates of Poly-propylene glycols, tripropylene glycol diacrylate, Viscoat 295, tetramethylol methane tetraacrylate.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107082875A (en) * | 2017-06-06 | 2017-08-22 | 无锡阿科力科技股份有限公司 | Heat resistant type unsaturated polyester resin and preparation method thereof |
| CN107099227A (en) * | 2017-05-17 | 2017-08-29 | 恒昌涂料（惠阳）有限公司 | The unsaturated polyester resin of solid content 100% and the net taste PE varnish of low VOC |
| CN107141420A (en) * | 2017-06-06 | 2017-09-08 | 无锡阿科力科技股份有限公司 | Without styrene UPR with low shrinkage resin and preparation method thereof |
| CN107216427A (en) * | 2017-06-15 | 2017-09-29 | 中山市大涂料有限公司 | A kind of block modified polyurethane/acrylate emulsion of unsaturated polyester resin and preparation method thereof |
| CN107663264A (en) * | 2017-09-21 | 2018-02-06 | 广东溢达纺织有限公司 | A kind of unsaturated polyester resin without styrene and preparation method and application |
| CN107955113A (en) * | 2017-11-29 | 2018-04-24 | 华南理工大学 | A kind of flexible unsaturated polyester resin of no styrene and preparation method thereof |
| CN111253557A (en) * | 2020-03-19 | 2020-06-09 | 北华航天工业学院 | Preparation method of heat-resistant unsaturated polyester resin |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1842885A1 (en) * | 2006-04-05 | 2007-10-10 | Ivm S.R.L. | styrene-free varnish based on polyunsaturated polyester resins |
| CN101851322A (en) * | 2010-04-20 | 2010-10-06 | 华东理工大学华昌聚合物有限公司 | Process for synthesizing unsaturated polyester resin of isocyanate block copolymerization |
| CN104628966A (en) * | 2015-01-23 | 2015-05-20 | 福建农林大学 | Plant fiber reinforced environment-friendly unsaturated polyester composite material |
-
2015
- 2015-12-31 CN CN201511014282.1A patent/CN105622858B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1842885A1 (en) * | 2006-04-05 | 2007-10-10 | Ivm S.R.L. | styrene-free varnish based on polyunsaturated polyester resins |
| CN101851322A (en) * | 2010-04-20 | 2010-10-06 | 华东理工大学华昌聚合物有限公司 | Process for synthesizing unsaturated polyester resin of isocyanate block copolymerization |
| CN104628966A (en) * | 2015-01-23 | 2015-05-20 | 福建农林大学 | Plant fiber reinforced environment-friendly unsaturated polyester composite material |
Non-Patent Citations (2)
| Title |
|---|
| COUSINET, SYLVAIN ET AL.,: ""Biobased Vinyl Levulinate as Styrene Replacement for Unsaturated Polyester Resins"", 《JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY》 * |
| 钟荆祥等: ""不饱和聚酯改性丙烯酸树脂"", 《上海涂料》 * |
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|---|---|---|---|---|
| CN107099227A (en) * | 2017-05-17 | 2017-08-29 | 恒昌涂料（惠阳）有限公司 | The unsaturated polyester resin of solid content 100% and the net taste PE varnish of low VOC |
| CN107099227B (en) * | 2017-05-17 | 2019-07-05 | 恒昌涂料（惠阳）有限公司 | 100% unsaturated polyester resin of solid content and low VOC ordor removing PE varnish |
| CN107082875A (en) * | 2017-06-06 | 2017-08-22 | 无锡阿科力科技股份有限公司 | Heat resistant type unsaturated polyester resin and preparation method thereof |
| CN107141420A (en) * | 2017-06-06 | 2017-09-08 | 无锡阿科力科技股份有限公司 | Without styrene UPR with low shrinkage resin and preparation method thereof |
| CN107141420B (en) * | 2017-06-06 | 2019-04-30 | 无锡阿科力科技股份有限公司 | Without styrene UPR with low shrinkage resin and preparation method thereof |
| CN107216427A (en) * | 2017-06-15 | 2017-09-29 | 中山市大涂料有限公司 | A kind of block modified polyurethane/acrylate emulsion of unsaturated polyester resin and preparation method thereof |
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| CN107663264B (en) * | 2017-09-21 | 2019-09-10 | 广东溢达纺织有限公司 | A kind of unsaturated polyester resin and the preparation method and application thereof without styrene |
| CN107955113A (en) * | 2017-11-29 | 2018-04-24 | 华南理工大学 | A kind of flexible unsaturated polyester resin of no styrene and preparation method thereof |
| CN111253557A (en) * | 2020-03-19 | 2020-06-09 | 北华航天工业学院 | Preparation method of heat-resistant unsaturated polyester resin |
| CN111253557B (en) * | 2020-03-19 | 2022-04-15 | 北华航天工业学院 | Preparation method of heat-resistant unsaturated polyester resin |
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