CN102181015B - Method for synthesizing reactive halogen-free flame-retardant unsaturated polyester resin - Google Patents
Method for synthesizing reactive halogen-free flame-retardant unsaturated polyester resin Download PDFInfo
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Abstract
The invention discloses a method for synthesizing reactive halogen-free flame-retardant unsaturated polyester resin. The method is characterized by taking dihydric alcohol, dibasic acid or dibasic acid anhydride, reactive phosphorus flame retardants such as 2- carboxyethyl (phenyl) phosphinic acid and phenyl hydroxymethyl phosphinic acid, and reactive silicon flame retardants such as dihydroxy diphenyl silane and dihydroxy dimethyl silane as basic materials, conducting esterification and polycondensation under the conditions of catalysts such as dibutyltin oxide and sodium acetate, and then adding diluent, thus preparing the halogen-free flame-retardant unsaturated polyester resin. The resin prepared by the method is especially applicable to the production of unsaturated polyester resin moulding compounds, glass fiber reinforced plastics and electrical plastic products, can meet the requirements of products on flame retarding and lightweight and has good properties.
Description
Technical field
The invention belongs to the preparation method of macromolecular compound, relate to a kind of synthetic method of response type halogen-free flameproof unsaturated polyester resin.The response type halogen-free flameproof unsaturated polyester resin of the method preparation is specially adapted to the manufacturing of the matrix materials such as flame-retarded light unsaturated polyester die plastic or glass reinforced plastic, electrical plastics product.
Background technology
The huge advance made of the develop rapidly of world economy and society; how all to be faced with between resource exhaustion, environment protection and the Sustainable development strategic issue of balance, and to relate to the great moulding compound of market consumption that the present invention is correlated with and technology and the market trend of fibre glass product manufacture is environment friendly halogen-free fireproof, lightweight, the high mechanical electric performance of the products such as the matrix materials such as unsaturated polyester die plastic or glass reinforced plastic, electrical plastics.
At present, in the reaction-type flame-retarding unsaturated polyester of producing both at home and abroad, great majority use halogen containing flame-retardant, and synthetic unsaturated polyester has preferably flame retardant effect; This class halogenated flame retardant is introduced unsaturated polyester, produces a large amount of dense smoke and corrodibility toxic gas during burning, to environment and people's the larger threat of life security formation.
In the prior art, Chinese patent application publication number CN101514253A discloses environment-friendly flame-retarded unsaturated polyester resin and preparation method thereof, in 2-carboxyethyl phenyl Hypophosporous Acid, 50 (CEPPA) and the phenyl methylol Hypophosporous Acid, 50 (HMPPA) one or both are as the response type halogen-free flame retardants, and one or more in triphenylphosphate, triethyl phosphate, the methyl-phosphoric acid dimethyl ester are as additive flame retardant.If this class reactive flame retardant without dibasic alcohol anticipate and and the materials such as dibasic alcohol, diprotic acid add together the reactor direct reaction, phosphate group on CEPPA or the HMPPA is difficult to participate in reaction, it is difficult to cause the system acid number to descend, and the resin cast surface has the serious phenomenon that is clamminess.The adding of additive flame retardant has considerable influence to the mechanical property of unsaturated polyester, and the addition type organic fire-retardant also has the problem of a loss, can increase with the rising loss amount of envrionment temperature, affect flame retardant effect; Add styrenic crosslinker, vinylbenzene has wick effect, makes the unsaturated polyester resin flame-retardant effect undesirable.To sum up, existing reaction, interpolation mixed type phosphor-containing flame-proof unsaturated polyester resin have increasing tougheness because of most of addition type organic fire-retardants, the flexible increase of goods, rigidity are descended, and organic fire-retardant also has the problem of a loss, envrionment temperature has considerable influence to loss, temperature is high, and the loss amount is just large, affects flame retardant effect.
Summary of the invention
Purpose of the present invention is intended to overcome deficiency of the prior art, and the synthetic method of the response type halogen-free flameproof unsaturated polyester resin of a kind of phosphorous, nitrogen, silicon is provided.Adopt the excellent property of the response type halogen-free flameproof unsaturated polyester resin of present method preparation.
Content of the present invention is: a kind of synthetic method of response type halogen-free flameproof unsaturated polyester resin is characterized in that may further comprise the steps:
A, batching:
Raw material composition and mass ratio by dibasic alcohol 20～30 mass parts, diprotic acid or dibasic acid anhydride 25～35 mass parts, phosphorus flame retardant 8～20 mass parts, silicon-series five-retardant 2～7 mass parts, catalyzer 0.02～0.05 mass parts, stopper 0.014～0.04 mass parts, thinner 30～40 mass parts are got each component raw material;
B, preparation prepolymer:
Dibasic alcohol 10～15 mass parts and phosphorus flame retardant 8～20 mass parts are mixed, after 140～160 ℃ of temperature are reacted 3～5 hours down, again-0.093～-cool to room temperature after reacting 2～4 hours under the 0.09MPa vacuum tightness, 160～180 ℃ of conditions, make prepolymer;
C, preparation flame-retarded unsaturated polyester resin:
Dibasic alcohol 10～15 mass parts with remainder, diprotic acid or dibasic acid anhydride 25～35 mass parts, catalyzer 0.02～0.05 mass parts, silicon-series five-retardant 2～7 mass parts and stopper 0.007～0.02 mass parts Hybrid Heating are warmed up to 140～150 ℃, be incubated 0.5～1 hour, progressively be warmed up to 200～205 ℃ with 6～8 hours, be incubated 2～4 hours, add again the prepolymer that step b makes, heated to gradually 200～205 ℃ with 2～3 hours, begin decompression vacuum pumping 200～205 ℃ of lower reactions after 1～2 hour, make reactor vacuum tightness reach-0.093～-0.09MPa, be reaction end until acid number drops to 30～40mgKOH/g, cool to 100～120 ℃, add remaining stopper 0.007～0.02 mass parts and thinner 30～40 mass parts and mix, namely make response type halogen-free flameproof unsaturated polyester resin;
Described dibasic alcohol is two or more the mixture in ethylene glycol, 1,2-PD, neopentyl glycol, Diethylene Glycol, the dipropylene glycol;
Described diprotic acid or dibasic acid anhydride are two or more the mixture in fumaric acid, MALEIC ANHYDRIDE, Tetra hydro Phthalic anhydride, m-phthalic acid, the hexanodioic acid;
Described phosphorus flame retardant is one or more the mixture in 2-carboxyethyl phenyl Hypophosporous Acid, 50 (CEPPA), phenyl methylol Hypophosporous Acid, 50 (HMPPA), the benzenephosphonic acid benzenedio ester;
Described silicon-series five-retardant is one or more the mixture in hexichol dihydroxy silane, dihydroxy dimethylsilane, the phenyl methyl dihydroxy silane;
Described catalyzer is one or more the mixture in Dibutyltin oxide, sodium acetate, the two lauric acid butyl tin;
Described stopper is Resorcinol;
Described thinner is the mixture of vinylbenzene and trialkenyl methyl three isocyanuric acid fat (TAIC), and vinylbenzene: the mass ratio of trialkenyl methyl three isocyanuric acid fat is 1:0.1～1.
In the content of the present invention: described diprotic acid or dibasic acid anhydride are preferably the mixture of unsaturated dibasic acid or acid anhydrides and monounsaturated dicarboxylic acid or acid anhydrides, and unsaturated dibasic acid or acid anhydrides and monounsaturated dicarboxylic acid or acid anhydrides quality proportioning are 1:0～0.2; Described unsaturated dibasic acid acid or acid anhydrides are MALEIC ANHYDRIDE or fumaric acid; Described monounsaturated dicarboxylic acid or acid anhydrides are Tetra hydro Phthalic anhydride, m-phthalic acid or hexanodioic acid.
In the content of the present invention: described dibasic alcohol is the mixture of 1,2-PD and ethylene glycol preferably, and the quality proportioning of 1,2-PD and ethylene glycol is 1:0.25～0.62.
In the content of the present invention: the quality proportioning of described thinner vinylbenzene and trialkenyl methyl three isocyanuric acid fat is 1:0.23～1 preferably.
Compared with prior art, the present invention has following characteristics and beneficial effect:
(1) the present invention introduces phosphorus, element silicon in the unsaturated polyester molecular chain by copolymerization, when curable unsaturated polyester the nitrogen element in the nitrogenous linking agent is introduced molecular chain, forms the three dimensional structure that contains phosphorus, nitrogen, element silicon.Its fire retardant mechanism is: when phosphorous in the molecular structure behind the curable unsaturated polyester, nitrogen, element silicon, at high temperature, the nitrogen element can catch the free radical because of pyrolytic decomposition, stops polymer segment further to decompose; The formation of charcoal is facilitated in phosphoric meeting catalysis, silicon then increases the thermostability of these charcoal layers, thereby performance phosphorus, nitrogen, silicon cooperative flame retardant effect, relatively common unsaturated polyester improves oxygen index 6.3%～10%, embodiment has reached 26.1%～29.8%, and the unsaturated polyester product of optimization formula actual production can reach the flame retardant rating of FV0 level fully;
(2) although the present invention has introduced nitrogen, phosphorus, element silicon simultaneously in the unsaturated polyester resin molecular chain, mechanical property on unsaturated polyester resin moulding compound, glass reinforced plastic and electrical plastics product does not have impact substantially, and the mechanical property of the unsaturated polyester resin moulding compound product that the embodiment prescription is produced also is improved;
(3) after the present invention uses dibasic alcohol that phosphorus flame retardant is anticipated, after finishing, the esterifications such as dibasic alcohol, diprotic acid, silicon-series five-retardant add, just can guarantee that phosphorus flame retardant fully reacts, the system acid number can drop to ideal range, and can there be the phenomenon that is clamminess in the resin cast surface;
(4) product preparation process of the present invention is simple, and good product quality is for industrial production provides a kind of feasible synthetic method, practical.
Embodiment
Embodiment given below intends so that the invention will be further described; but can not be interpreted as it is limiting the scope of the invention; the person skilled in art to some nonessential improvement and adjustment that the present invention makes, still belongs to protection scope of the present invention according to the content of the invention described above.
Embodiment 1:
(1) in being furnished with the 1000ml there-necked flask of stirrer, thermopair and rectifying tower, adds 100 gram ethylene glycol, 80 gram CEPPA, 140 ℃～160 ℃ lower reactions 3～5 hours, in-0.093MPa vacuum tightness, react after 2～4 hours under 160 ℃ of conditions and obtain prepolymer 1, it is stand-by to drop to room temperature.
(2) at another with stirrer, add 80 grams 1 in the 1000ml there-necked flask of thermopair and rectifying tower, the 2-propylene glycol, 20 gram Diethylene Glycols, 210 gram MALEIC ANHYDRIDE, 40 gram Tetra hydro Phthalic anhydrides, 0.2 gram Dibutyltin oxide, 20 gram hexichol dihydroxy silane, 0.07 gram Resorcinol, heat to 140 ℃, be incubated 1 hour, progressively be warmed up to 200 ℃ with 6～8 hours, be incubated 2～4 hours, add all prepolymers 1 that (1) obtains, heat to gradually 200 ℃, react decompression vacuum pumping after 1 hour, vacuum tightness is-0.093MPa, be reaction end until resinous acid value drops to 30～40mgKOH/g, cool to 120 ℃, add 0.07 gram Resorcinol, 300 gram thinner (vinylbenzene: TAIC==1:0.23), stirring cools to 40 ℃ of dischargings, namely obtains the pistac transparent unsaturated polyester resin of this patent invention scheme.
Embodiment 2:
(1) in being furnished with the 1000ml there-necked flask of stirrer, thermopair and rectifying tower, adds 140 gram ethylene glycol, 10 gram neopentyl glycol, 200 gram CEPPA, 140 ℃～160 ℃ lower reactions 3～5 hours,-0.093MPa vacuum tightness, react after 2～4 hours under 160 ℃ of conditions and obtain prepolymer 1, it is stand-by to drop to room temperature.
(2) at another with stirrer, add 150 grams 1 in the 1000ml there-necked flask of thermopair and rectifying tower, the 2-propylene glycol, 300 gram MALEIC ANHYDRIDE, 20 gram m-phthalic acids, 10 gram Tetra hydro Phthalic anhydrides, 20 diacid of restraining oneself, 0.3 gram Dibutyltin oxide, 0.2 restrain two lauric acid butyl tin, 70 gram hexichol dihydroxy silane, 0.2 gram Resorcinol, heat to 140 ℃, be incubated 1 hour, progressively be warmed up to 200 ℃ with 6～8 hours, be incubated 2～4 hours, add all prepolymers 1 that (1) obtains, heat to gradually 200 ℃, react decompression vacuum pumping after 1 hour, vacuum tightness is-0.093MPa, be reaction end until resinous acid value drops to 30～40mgKOH/g, cool to 120 ℃, add 0.2 gram Resorcinol, 370 gram thinner (vinylbenzene: TAIC==1:1), stirring cools to 40 ℃ of dischargings, namely obtains the pistac transparent unsaturated polyester resin of this patent invention scheme.
Embodiment 3:
(1) in being furnished with the 1000ml there-necked flask of stirrer, thermopair and rectifying tower, adds 130 gram ethylene glycol, 10 gram Diethylene Glycols, 150 gram CEPPA, 140 ℃～160 ℃ lower reactions 3～5 hours,-0.093MPa vacuum tightness, react after 2～4 hours under 160 ℃ of conditions and obtain prepolymer 1, it is stand-by to drop to room temperature.
(2) at another with stirrer, add 140 grams 1 in the 1000ml there-necked flask of thermopair and rectifying tower, the 2-propylene glycol, 10 gram neopentyl glycol, 320 gram MALEIC ANHYDRIDE, 0.4 gram Dibutyltin oxide, 23 gram hexichol dihydroxy silane, 0.1 gram Resorcinol, heat to 140 ℃, be incubated 1 hour, progressively be warmed up to 200 ℃ with 6～8 hours, be incubated 2～4 hours, add all prepolymers 1 that (1) obtains, heat to gradually 200 ℃, react decompression vacuum pumping after 1 hour, vacuum tightness is-0.093MPa, be reaction end until resinous acid value drops to 30～40mgKOH/g, cool to 120 ℃, add 0.1 gram Resorcinol, 350 gram thinner (vinylbenzene: TAIC==1:0.25), stirring cools to 40 ℃ of dischargings, namely obtains the pistac transparent unsaturated polyester resin of this patent invention scheme.
Embodiment 4:
(1) in being furnished with the 1000ml there-necked flask of stirrer, thermopair and rectifying tower, adds 110 gram ethylene glycol, 20 gram dipropylene glycols, 140 gram HMPPA, 140 ℃～160 ℃ lower reactions 3～5 hours,-0.093MPa vacuum tightness, react after 2～4 hours under 160 ℃ of conditions and obtain prepolymer 1, it is stand-by to drop to room temperature.
(2) at another with stirrer, add 140 grams 1 in the 1000ml there-necked flask of thermopair and rectifying tower, the 2-propylene glycol, 5 gram neopentyl glycol, 320 gram MALEIC ANHYDRIDE, 20 gram hexichol dihydroxy silane, 10 gram aminomethyl phenyl dihydroxy silane, 0.4 gram Dibutyltin oxide, 0.08 gram Resorcinol, heat to 140 ℃, be incubated 1 hour, progressively be warmed up to 200 ℃ with 6～8 hours, be incubated 2～4 hours, add all prepolymers 1 that (1) obtains, heat to gradually 200 ℃, react decompression vacuum pumping after 1 hour, vacuum tightness is-0.093MPa, be reaction end until resinous acid value drops to 30～40mgKOH/g, cool to 120 ℃, add 0.12 gram Resorcinol, 400 gram thinner (vinylbenzene: TAIC==1:0.27), stirring cools to 40 ℃ of dischargings, namely obtains the pistac transparent unsaturated polyester resin of this patent invention scheme.
Embodiment 5:
(1) in being furnished with the 1000ml there-necked flask of stirrer, thermopair and rectifying tower, adds 130 gram ethylene glycol, 140 gram HMPPA, 30 gram benzenephosphonic acid benzenedio esters, 140 ℃～160 ℃ lower reactions 3～5 hours,-0.093MPa vacuum tightness, react after 2～4 hours under 160 ℃ of conditions and obtain prepolymer 1, it is stand-by to drop to room temperature.
(2) at another with stirrer, add 110 grams 1 in the 1000ml there-necked flask of thermopair and rectifying tower, the 2-propylene glycol, 3 gram Diethylene Glycols, 3 gram dipropylene glycols, 320 gram MALEIC ANHYDRIDE, 35 gram hexichol dihydroxy silane, 0.3 gram Dibutyltin oxide, 0.12 gram Resorcinol, heat to 140 ℃, be incubated 1 hour, progressively be warmed up to 200 ℃ with 6～8 hours, be incubated 2～4 hours, add all prepolymers 1 that (1) obtains, heat to gradually 200 ℃, react decompression vacuum pumping after 1 hour, vacuum tightness is-0.093MPa, be reaction end until resinous acid value drops to 30～40mgKOH/g, cool to 120 ℃, add 0.16 gram Resorcinol, 380 gram thinner (vinylbenzene: TAIC==1:0.33), stirring cools to 40 ℃ of dischargings, namely obtains the pistac transparent unsaturated polyester resin of this patent invention scheme.
Embodiment 6:
(1) in being furnished with the 1000ml there-necked flask of stirrer, thermopair and rectifying tower, adds 110 gram ethylene glycol, 15 gram Diethylene Glycols, 200 gram CEPPA, 140 ℃～160 ℃ lower reactions 3～5 hours,-0.093MPa vacuum tightness, react after 2～4 hours under 160 ℃ of conditions and obtain prepolymer 1, it is stand-by to drop to room temperature.
(2) at another with stirrer, add 150 grams 1 in the 1000ml there-necked flask of thermopair and rectifying tower, the 2-propylene glycol, 300 gram MALEIC ANHYDRIDE, 15 gram fumaric acid, 42 gram hexichol dihydroxy silane, 0.5 gram Dibutyltin oxide, 0.11 gram Resorcinol, heat to 140 ℃, be incubated 1 hour, progressively be warmed up to 200 ℃ with 6～8 hours, be incubated 2～4 hours, add all prepolymers 1 that (1) obtains, heat to gradually 200 ℃, react decompression vacuum pumping after 1 hour, vacuum tightness is-0.093MPa, be reaction end until resinous acid value drops to 30～40mgKOH/g, cool to 120 ℃, add 0.15 gram Resorcinol, 400 gram thinners (vinylbenzene: TAIC==1:0.4) gram vinylbenzene, stirring cools to 40 ℃ of dischargings, namely obtains the pistac transparent unsaturated polyester resin of this patent invention scheme.
Embodiment 7:
(1) in being furnished with the 1000ml there-necked flask of stirrer, thermopair and rectifying tower, adds 130 gram ethylene glycol, 130 gram CEPPA, 20 gram benzenephosphonic acid benzenedio esters, 140 ℃～160 ℃ lower reactions 3～5 hours,-0.093MPa vacuum tightness, react after 2～4 hours under 160 ℃ of conditions and obtain prepolymer 1, it is stand-by to drop to room temperature.
(2) at another with stirrer, add 116 grams 1 in the 1000ml there-necked flask of thermopair and rectifying tower, the 2-propylene glycol, 10 gram dipropylene glycols, 300 gram MALEIC ANHYDRIDE, 10 gram m-phthalic acids, 30 gram hexichol dihydroxy silane, 10 gram dihydroxy dimethylsilane, 10 gram aminomethyl phenyl dihydroxy silane, 0.3 gram Dibutyltin oxide, 0.1 gram Resorcinol, heat to 140 ℃, be incubated 1 hour, progressively be warmed up to 200 ℃ with 6～8 hours, be incubated 2～4 hours, add all prepolymers 1 that (1) obtains, heat to gradually 200 ℃, react decompression vacuum pumping after 1 hour, vacuum tightness is-0.093MPa, be reaction end until resinous acid value drops to 30～40mgKOH/g, cool to 120 ℃, add 0.2 gram Resorcinol, 400 gram thinner (vinylbenzene: TAIC==1:0.48), stirring cools to 40 ℃ of dischargings, namely obtains the pistac transparent unsaturated polyester resin of this patent invention scheme.
Embodiment 8:
(1) in being furnished with the 1000ml there-necked flask of stirrer, thermopair and rectifying tower, adds 130 gram ethylene glycol, 120 gram CEPPA, 50 gram benzenephosphonic acid benzenedio esters, 140 ℃～160 ℃ lower reactions 3～5 hours,-0.093MPa vacuum tightness, react after 2～4 hours under 160 ℃ of conditions and obtain prepolymer 1, it is stand-by to drop to room temperature.
(2) at another with stirrer, add 130 grams 1 in the 1000ml there-necked flask of thermopair and rectifying tower, the 2-propylene glycol, 300 gram MALEIC ANHYDRIDE, 10 gram Tetra hydro Phthalic anhydrides, 60 gram aminomethyl phenyl dihydroxy silane, 0.4 gram Dibutyltin oxide, 0.15 gram Resorcinol, heat to 140 ℃, be incubated 1 hour, progressively be warmed up to 200 ℃ with 6～8 hours, be incubated 2～4 hours, add all prepolymers 1 that (1) obtains, heat to gradually 200 ℃, react decompression vacuum pumping after 1 hour, vacuum tightness is-0.093MPa, be reaction end until resinous acid value drops to 30～40mgKOH/g, cool to 120 ℃, add 0.15 gram Resorcinol, 400 gram thinner (vinylbenzene: TAIC==1:0.6), stirring cools to 40 ℃ of dischargings, namely obtains the pistac transparent unsaturated polyester resin of this patent invention scheme.
Embodiment 9:
(1) in being furnished with the 1000ml there-necked flask of stirrer, thermopair and rectifying tower, adds 100 gram ethylene glycol, 20 gram dipropylene glycols, 120 gram CEPPA, 80 gram benzenephosphonic acid benzenedio esters, 140 ℃～160 ℃ lower reactions 3～5 hours,-0.093MPa vacuum tightness, react after 2～4 hours under 160 ℃ of conditions and obtain prepolymer 1, it is stand-by to drop to room temperature.
(2) at another with stirrer, add 130 grams 1 in the 1000ml there-necked flask of thermopair and rectifying tower, the 2-propylene glycol, 5 gram neopentyl glycol, 5 gram dipropylene glycols, 300 gram MALEIC ANHYDRIDE, 15 gram Tetra hydro Phthalic anhydrides, 60 gram hexichol dihydroxy silane, 20 gram aminomethyl phenyl dihydroxy silane, 0.2 gram Dibutyltin oxide, 0.1 gram sodium acetate, 0.2 restrain two lauric acid butyl tin, 0.11 gram Resorcinol, heat to 140 ℃, be incubated 1 hour, progressively be warmed up to 200 ℃ with 6～8 hours, be incubated 2～4 hours, add all prepolymers 1 that (1) obtains, heat to gradually 200 ℃, react decompression vacuum pumping after 1 hour, vacuum tightness is-0.093MPa, be reaction end until resinous acid value drops to 30～40mgKOH/g, cool to 120 ℃, add 0.11 gram Resorcinol, 380 gram thinner (vinylbenzene: TAIC==1:0.7), stirring cools to 40 ℃ of dischargings, namely obtains the pistac transparent unsaturated polyester resin of this patent invention scheme.
Embodiment 10:
(1) in being furnished with the 1000ml there-necked flask of stirrer, thermopair and rectifying tower, adds 120 gram ethylene glycol, 20 gram CEPPA, 60 gram HMPPA, 140 ℃～160 ℃ lower reactions 3～5 hours,-0.093MPa vacuum tightness, react after 2～4 hours under 160 ℃ of conditions and obtain prepolymer 1, it is stand-by to drop to room temperature.
(2) at another with stirrer, add 130 grams 1 in the 1000ml there-necked flask of thermopair and rectifying tower, the 2-propylene glycol, 10 gram dipropylene glycols, 320 gram MALEIC ANHYDRIDE, 30 diacid of restraining oneself, 0.1 gram Dibutyltin oxide, 0.1 gram sodium acetate, 10 gram hexichol dihydroxy silane, 10 gram dihydroxy dimethylsilane, 0.07 gram Resorcinol, heat to 140 ℃, be incubated 1 hour, progressively be warmed up to 200 ℃ with 6～8 hours, be incubated 2～4 hours, add all prepolymers 1 that (1) obtains, heat to gradually 200 ℃, react decompression vacuum pumping after 1 hour, vacuum tightness is-0.093MPa, be reaction end until resinous acid value drops to 30～40mgKOH/g, cool to 120 ℃, add 0.2 gram Resorcinol, 365 gram thinner (vinylbenzene: TAIC==1:1), stirring cools to 40 ℃ of dischargings, namely obtains the pistac transparent unsaturated polyester resin of this patent invention scheme.
Embodiment 11:
(1) in being furnished with the 1000ml there-necked flask of stirrer, thermopair and rectifying tower, adds 130 gram ethylene glycol, 20 gram Diethylene Glycols, 200 gram CEPPA, 140 ℃～160 ℃ lower reactions 3～5 hours,-0.093MPa vacuum tightness, react after 2～4 hours under 160 ℃ of conditions and obtain prepolymer 1, it is stand-by to drop to room temperature.
(2) at another with stirrer, add 150 grams 1 in the 1000ml there-necked flask of thermopair and rectifying tower, the 2-propylene glycol, 280 gram MALEIC ANHYDRIDE, 40 gram m-phthalic acids, 30 diacid of restraining oneself, 0.3 gram Dibutyltin oxide, 0.2 restrain two lauric acid butyl tin, 70 gram hexichol dihydroxy silane, 0.1 gram Resorcinol, heat to 140 ℃, be incubated 1 hour, progressively be warmed up to 200 ℃ with 6～8 hours, be incubated 2～4 hours, add all prepolymers 1 that (1) obtains, heat to gradually 200 ℃, react decompression vacuum pumping after 1 hour, vacuum tightness is-0.093MPa, be reaction end until resinous acid value drops to 30～40mgKOH/g, cool to 120 ℃, add 0.1 gram Resorcinol, 400 gram thinner (vinylbenzene: TAIC==1:1), stirring cools to 40 ℃ of dischargings, namely obtains the pistac transparent unsaturated polyester resin of this patent invention scheme.
Embodiment 12:
(1) in being furnished with the 1000ml there-necked flask of stirrer, thermopair and rectifying tower, adds 120 gram ethylene glycol, 50 gram CEPPA, 80 gram HMPPA, 140 ℃～160 ℃ lower reactions 3～5 hours,-0.093MPa vacuum tightness, react after 2～4 hours under 160 ℃ of conditions and obtain prepolymer 1, it is stand-by to drop to room temperature.
(2) at another with stirrer, add 135 grams 1 in the 1000ml there-necked flask of thermopair and rectifying tower, the 2-propylene glycol, 5 gram neopentyl glycol, 320 gram MALEIC ANHYDRIDE, 30 gram Tetra hydro Phthalic anhydrides, 0.15 gram Dibutyltin oxide, 0.15 gram sodium acetate, 30 gram aminomethyl phenyl dihydroxy silane, 20 gram dihydroxy dimethylsilane, 0.2 gram Resorcinol, heat to 140 ℃, be incubated 1 hour, progressively be warmed up to 200 ℃ with 6～8 hours, be incubated 2～4 hours, add all prepolymers 1 that (1) obtains, heat to gradually 200 ℃, react decompression vacuum pumping after 1 hour, vacuum tightness is-0.093MPa, be reaction end until resinous acid value drops to 30～40mgKOH/g, cool to 120 ℃, add 0.15 gram Resorcinol, 400 gram thinner (vinylbenzene: TAIC==1:0.7), stirring cools to 40 ℃ of dischargings, namely obtains the pistac transparent unsaturated polyester resin of this patent invention scheme.
Embodiment 13:
(1) in being furnished with the 1000ml there-necked flask of stirrer, thermopair and rectifying tower, adds 50 gram ethylene glycol, 50 grams 1,2-propylene glycol, 100 gram HMPPA, 100 gram CEPPA, 140 ℃～160 ℃ lower reactions 3～5 hours,-0.093MPa vacuum tightness, react after 2～4 hours under 160 ℃ of conditions and obtain prepolymer 1, it is stand-by to drop to room temperature.
(2) at another with stirrer, add 150 grams 1 in the 1000ml there-necked flask of thermopair and rectifying tower, the 2-propylene glycol, 310 gram MALEIC ANHYDRIDE, 70 gram hexichol dihydroxy silane, 10 gram aminomethyl phenyl dihydroxy silane, 0.3 gram Dibutyltin oxide, 0.1 gram Resorcinol, heat to 140 ℃, be incubated 1 hour, progressively be warmed up to 200 ℃ with 6～8 hours, be incubated 2～4 hours, add all prepolymers 1 that (1) obtains, heat to gradually 200 ℃, react decompression vacuum pumping after 1 hour, vacuum tightness is-0.093MPa, be reaction end until resinous acid value drops to 30～40mgKOH/g, cool to 120 ℃, add 0.12 gram Resorcinol, 400 gram thinner (vinylbenzene: TAIC==1:1), stirring cools to 40 ℃ of dischargings, namely obtains the pistac transparent unsaturated polyester resin of this patent invention scheme.
Embodiment 14:
(1) in being furnished with the 1000ml there-necked flask of stirrer, thermopair and rectifying tower, adds 100 gram ethylene glycol, 12 grams 1,2-propylene glycol, 150 gram CEPPA, 140 ℃～160 ℃ lower reactions 3～5 hours,-0.093MPa vacuum tightness, react after 2～4 hours under 160 ℃ of conditions and obtain prepolymer 1, it is stand-by to drop to room temperature.
(2) at another with stirrer, add 150 grams 1 in the 1000ml there-necked flask of thermopair and rectifying tower, the 2-propylene glycol, 315 gram MALEIC ANHYDRIDE, 42 gram hexichol dihydroxy silane, 0.5 gram Dibutyltin oxide, 0.13 gram Resorcinol, heat to 140 ℃, be incubated 1 hour, progressively be warmed up to 200 ℃ with 6～8 hours, be incubated 2～4 hours, add all prepolymers 1 that (1) obtains, heat to gradually 200 ℃, react decompression vacuum pumping after 1 hour, vacuum tightness is-0.093MPa, be reaction end until resinous acid value drops to 30～40mgKOH/g, cool to 120 ℃, add 0.15 gram Resorcinol, 400 gram thinners (vinylbenzene: TAIC==1:0.4) gram vinylbenzene, stirring cools to 40 ℃ of dischargings, namely obtains the pistac transparent unsaturated polyester resin of this patent invention scheme.
Embodiment 15:
(1) in being furnished with the 1000ml there-necked flask of stirrer, thermopair and rectifying tower, adds 90 gram ethylene glycol, 50 grams 1,2-propylene glycol, 50 gram CEPPA, 80 gram HMPPA, 140 ℃～160 ℃ lower reactions 3～5 hours,-0.093MPa vacuum tightness, react after 2～4 hours under 160 ℃ of conditions and obtain prepolymer 1, it is stand-by to drop to room temperature.
(2) at another with stirrer, add 150 grams 1 in the 1000ml there-necked flask of thermopair and rectifying tower, the 2-propylene glycol, 340 gram MALEIC ANHYDRIDE, 10 gram Tetra hydro Phthalic anhydrides, 0.15 gram Dibutyltin oxide, 0.1 gram sodium acetate, 20 gram aminomethyl phenyl dihydroxy silane, 20 gram dihydroxy dimethylsilane, 0.12 gram Resorcinol, heat to 140 ℃, be incubated 1 hour, progressively be warmed up to 200 ℃ with 6～8 hours, be incubated 2～4 hours, add all prepolymers 1 that (1) obtains, heat to gradually 200 ℃, react decompression vacuum pumping after 1 hour, vacuum tightness is-0.093MPa, be reaction end until resinous acid value drops to 30～40mgKOH/g, cool to 120 ℃, add 0.15 gram Resorcinol, 400 gram thinner (vinylbenzene: TAIC==1:0.7), stirring cools to 40 ℃ of dischargings, namely obtains the pistac transparent unsaturated polyester resin of this patent invention scheme.
Embodiment 16:
(1) in being furnished with the 1000ml there-necked flask of stirrer, thermopair and rectifying tower, adds 140 grams 1,2-propylene glycol, 130 gram CEPPA, 20 gram benzenephosphonic acid benzenedio esters, 140 ℃～160 ℃ lower reactions 3～5 hours,-0.093MPa vacuum tightness, react after 2～4 hours under 160 ℃ of conditions and obtain prepolymer 1, it is stand-by to drop to room temperature.
(2) at another with stirrer, add 126 grams 1 in the 1000ml there-necked flask of thermopair and rectifying tower, the 2-propylene glycol, 24 gram neopentyl glycol, 300 gram MALEIC ANHYDRIDE, 10 gram m-phthalic acids, 30 gram hexichol dihydroxy silane, 10 gram dihydroxy dimethylsilane, 10 gram aminomethyl phenyl dihydroxy silane, 0.3 gram Dibutyltin oxide, 0.1 gram Resorcinol, heat to 140 ℃, be incubated 1 hour, progressively be warmed up to 200 ℃ with 6～8 hours, be incubated 2～4 hours, add all prepolymers 1 that (1) obtains, heat to gradually 200 ℃, react decompression vacuum pumping after 1 hour, vacuum tightness is-0.093MPa, be reaction end until resinous acid value drops to 30～40mgKOH/g, cool to 120 ℃, add 0.2 gram Resorcinol, 400 gram thinner (vinylbenzene: TAIC==1:0.5), stirring cools to 40 ℃ of dischargings, namely obtains the pistac transparent unsaturated polyester resin of this patent invention scheme.
Embodiment 17:
(1) in being furnished with the 1000ml there-necked flask of stirrer, thermopair and rectifying tower, adds 100 gram ethylene glycol, 170 gram benzenephosphonic acid benzenedio esters, 140 ℃～160 ℃ lower reactions 3～5 hours,-0.093MPa vacuum tightness, react after 2～4 hours under 160 ℃ of conditions and obtain prepolymer 1, it is stand-by to drop to room temperature.
(2) at another with stirrer, add 80 gram ethylene glycol in the 1000ml there-necked flask of thermopair and rectifying tower, 50 gram dipropylene glycols, 300 gram MALEIC ANHYDRIDE, 10 gram Tetra hydro Phthalic anhydrides, 60 gram aminomethyl phenyl dihydroxy silane, 0.4 gram Dibutyltin oxide, 0.15 gram Resorcinol, heat to 140 ℃, be incubated 1 hour, progressively be warmed up to 200 ℃ with 6～8 hours, be incubated 2～4 hours, add all prepolymers 1 that (1) obtains, heat to gradually 200 ℃, react decompression vacuum pumping after 1 hour, vacuum tightness is-0.093MPa, be reaction end until resinous acid value drops to 30～40mgKOH/g, cool to 120 ℃, add 0.15 gram Resorcinol, 400 gram thinner (vinylbenzene: TAIC==1:0.3), stirring cools to 40 ℃ of dischargings, namely obtains the pistac transparent unsaturated polyester resin of this patent invention scheme.
Embodiment 18:
(1) in being furnished with the 1000ml there-necked flask of stirrer, thermopair and rectifying tower, adds 130 grams 1,2-propylene glycol, 100 gram CEPPA, 80 gram benzenephosphonic acid benzenedio esters, 140 ℃～160 ℃ lower reactions 3～5 hours,-0.093MPa vacuum tightness, react after 2～4 hours under 160 ℃ of conditions and obtain prepolymer 1, it is stand-by to drop to room temperature.
(2) at another with stirrer, add 120 grams 1 in the 1000ml there-necked flask of thermopair and rectifying tower, the 2-propylene glycol, 20 gram Diethylene Glycols, 300 gram MALEIC ANHYDRIDE, 15 gram Tetra hydro Phthalic anhydrides, 50 gram hexichol dihydroxy silane, 20 gram aminomethyl phenyl dihydroxy silane, 0.1 gram Dibutyltin oxide, 0.2 gram sodium acetate, 0.2 restrain two lauric acid butyl tin, 0.11 gram Resorcinol, heat to 140 ℃, be incubated 1 hour, progressively be warmed up to 200 ℃ with 6～8 hours, be incubated 2～4 hours, add all prepolymers 1 that (1) obtains, heat to gradually 200 ℃, react decompression vacuum pumping after 1 hour, vacuum tightness is-0.093MPa, be reaction end until resinous acid value drops to 30～40mgKOH/g, cool to 120 ℃, add 0.11 gram Resorcinol, 380 gram thinner (vinylbenzene: TAIC==1:0.6), stirring cools to 40 ℃ of dischargings, namely obtains the pistac transparent unsaturated polyester resin of this patent invention scheme.
Embodiment 19:
(1) in being furnished with the 1000ml there-necked flask of stirrer, thermopair and rectifying tower, adds 120 gram ethylene glycol, 40 gram CEPPA, 60 gram HMPPA, 140 ℃～160 ℃ lower reactions 3～5 hours,-0.093MPa vacuum tightness, react after 2～4 hours under 160 ℃ of conditions and obtain prepolymer 1, it is stand-by to drop to room temperature.
(2) at another with stirrer, add 110 grams 1 in the 1000ml there-necked flask of thermopair and rectifying tower, the 2-propylene glycol, 30 gram dipropylene glycols, 310 gram MALEIC ANHYDRIDE, 40 diacid of restraining oneself, 0.1 gram Dibutyltin oxide, 0.1 gram sodium acetate, 15 gram hexichol dihydroxy silane, 15 gram dihydroxy dimethylsilane, 0.07 gram Resorcinol, heat to 140 ℃, be incubated 1 hour, progressively be warmed up to 200 ℃ with 6～8 hours, be incubated 2～4 hours, add all prepolymers 1 that (1) obtains, heat to gradually 200 ℃, react decompression vacuum pumping after 1 hour, vacuum tightness is-0.093MPa, be reaction end until resinous acid value drops to 30～40mgKOH/g, cool to 120 ℃, add 0.15 gram Resorcinol, 360 gram thinner (vinylbenzene: TAIC==1:1), stirring cools to 40 ℃ of dischargings, namely obtains the pistac transparent unsaturated polyester resin of this patent invention scheme.
Embodiment 20:
(1) in being furnished with the 1000ml there-necked flask of stirrer, thermopair and rectifying tower, adds 150 gram ethylene glycol, 190 gram CEPPA, 140 ℃～160 ℃ lower reactions 3～5 hours, in-0.093MPa vacuum tightness, react after 2～4 hours under 160 ℃ of conditions and obtain prepolymer 1, it is stand-by to drop to room temperature.
(2) at another with stirrer, add 130 grams 1 in the 1000ml there-necked flask of thermopair and rectifying tower, the 2-propylene glycol, 20 gram neopentyl glycol, 330 gram MALEIC ANHYDRIDE, 20 diacid of restraining oneself, 0.3 gram Dibutyltin oxide, 0.1 restrain two lauric acid butyl tin, 70 gram hexichol dihydroxy silane, 0.1 gram Resorcinol, heat to 140 ℃, be incubated 1 hour, progressively be warmed up to 200 ℃ with 6～8 hours, be incubated 2～4 hours, add all prepolymers 1 that (1) obtains, heat to gradually 200 ℃, react decompression vacuum pumping after 1 hour, vacuum tightness is-0.093MPa, be reaction end until resinous acid value drops to 30～40mgKOH/g, cool to 120 ℃, add 0.1 gram Resorcinol, 400 gram thinner (vinylbenzene: TAIC==1:0.9), stirring cools to 40 ℃ of dischargings, namely obtains the pistac transparent unsaturated polyester resin of this patent invention scheme.
Embodiment 21:
A kind of synthetic method of response type halogen-free flameproof unsaturated polyester resin may further comprise the steps:
A, batching:
Press dibasic alcohol 20 mass parts (unit: kilogram, rear with), the raw material of diprotic acid or dibasic acid anhydride 25 mass parts, phosphorus flame retardant 8 mass parts, silicon-series five-retardant 2 mass parts, catalyzer 0.02 mass parts, stopper 0.014 mass parts, thinner 30 mass parts forms and mass ratio is got each component raw material;
B, preparation prepolymer:
Dibasic alcohol 10 mass parts and phosphorus flame retardant 8 mass parts are mixed, in 140～160 ℃ of lower reactions of temperature after 3 hours, again-0.093～-0.09MPa vacuum tightness, 160～180 ℃ of conditions under reaction cool to room temperature after 2 hours, make prepolymer;
C, preparation flame-retarded unsaturated polyester resin:
Dibasic alcohol 10 mass parts with remainder, diprotic acid or dibasic acid anhydride 25 mass parts, catalyzer 0.02 mass parts, silicon-series five-retardant 2 mass parts and stopper 0.007 mass parts Hybrid Heating are warmed up to 140～150 ℃, be incubated 0.5 hour, progressively be warmed up to 200～205 ℃ with 6 hours, be incubated 2 hours, add again the prepolymer that step b makes, heated to gradually 200～205 ℃ with 2 hours, begin decompression vacuum pumping 200～205 ℃ of lower reactions after 1 hour, make reactor vacuum tightness reach-0.093～-0.09MPa, be reaction end until acid number drops to 30～40mgKOH/g, cool to 100～120 ℃, add remaining stopper 0.007 mass parts and thinner 30 mass parts and mix, namely make response type halogen-free flameproof unsaturated polyester resin;
Embodiment 22:
A kind of synthetic method of response type halogen-free flameproof unsaturated polyester resin may further comprise the steps:
A, batching:
Press dibasic alcohol 30 mass parts (unit: kilogram, rear with), the raw material of diprotic acid or dibasic acid anhydride 35 mass parts, phosphorus flame retardant 20 mass parts, silicon-series five-retardant 7 mass parts, catalyzer 0.05 mass parts, stopper 0.04 mass parts, thinner 40 mass parts forms and mass ratio is got each component raw material;
B, preparation prepolymer:
Dibasic alcohol 15 mass parts and phosphorus flame retardant 20 mass parts are mixed, in 140～160 ℃ of lower reactions of temperature after 5 hours, again-0.093～-0.09MPa vacuum tightness, 160～180 ℃ of conditions under reaction cool to room temperature after 4 hours, make prepolymer;
C, preparation flame-retarded unsaturated polyester resin:
Dibasic alcohol 15 mass parts with remainder, diprotic acid or dibasic acid anhydride 35 mass parts, catalyzer 0.05 mass parts, silicon-series five-retardant 7 mass parts and stopper 0.02 mass parts Hybrid Heating are warmed up to 140～150 ℃, be incubated 1 hour, progressively be warmed up to 200～205 ℃ with 6～8 hours, be incubated 4 hours, add again the prepolymer that step b makes, heated to gradually 200～205 ℃ with 2～3 hours, begin decompression vacuum pumping 200～205 ℃ of lower reactions after 2 hours, make reactor vacuum tightness reach-0.093～-0.09MPa, be reaction end until acid number drops to 30～40mgKOH/g, cool to 100～120 ℃, add remaining stopper 0.02 mass parts and thinner 40 mass parts and mix, namely make response type halogen-free flameproof unsaturated polyester resin;
Embodiment 23:
A kind of synthetic method of response type halogen-free flameproof unsaturated polyester resin may further comprise the steps:
A, batching:
Press dibasic alcohol 26 mass parts (unit: kilogram, rear with), the raw material of diprotic acid or dibasic acid anhydride 30 mass parts, phosphorus flame retardant 14 mass parts, silicon-series five-retardant 4 mass parts, catalyzer 0.03 mass parts, stopper 0.026 mass parts, thinner 35 mass parts forms and mass ratio is got each component raw material;
B, preparation prepolymer:
Dibasic alcohol 13 mass parts and phosphorus flame retardant 14 mass parts are mixed, in 140～160 ℃ of lower reactions of temperature after 4 hours, again-0.093～-0.09MPa vacuum tightness, 160～180 ℃ of conditions under reaction cool to room temperature after 3 hours, make prepolymer;
C, preparation flame-retarded unsaturated polyester resin:
Dibasic alcohol 13 mass parts with remainder, diprotic acid or dibasic acid anhydride 30 mass parts, catalyzer 0.03 mass parts, silicon-series five-retardant 4 mass parts and stopper 0.013 mass parts Hybrid Heating are warmed up to 140～150 ℃, be incubated 0.8 hour, progressively be warmed up to 200～205 ℃ with 6～8 hours, be incubated 3 hours, add again the prepolymer that step b makes, heated to gradually 200～205 ℃ with 2～3 hours, begin decompression vacuum pumping 200～205 ℃ of lower reactions after 1.5 hours, make reactor vacuum tightness reach-0.093～-0.09MPa, be reaction end until acid number drops to 30～40mgKOH/g, cool to 100～120 ℃, add remaining stopper 0.013 mass parts and thinner 35 mass parts and mix, namely make response type halogen-free flameproof unsaturated polyester resin;
Embodiment 24-30:
A kind of synthetic method of response type halogen-free flameproof unsaturated polyester resin may further comprise the steps:
A, batching:
Press dibasic alcohol 20～30 mass parts (unit: kilogram, rear with), the raw material of diprotic acid or dibasic acid anhydride 25～35 mass parts, phosphorus flame retardant 8～20 mass parts, silicon-series five-retardant 2～7 mass parts, catalyzer 0.02～0.05 mass parts, stopper 0.014～0.04 mass parts, thinner 30～40 mass parts forms and mass ratio is got each component raw material;
The consumption of each component among each embodiment (mass parts, unit: gram) see the following form:
B, preparation prepolymer:
The dibasic alcohol of 1/2 mass parts and phosphorus flame retardant are mixed, in 140～160 ℃ of lower reactions of temperature after 3～5 hours, again-0.093～-cool to room temperature after reacting 2～4 hours under the 0.09MPa vacuum tightness, 160～180 ℃ of conditions, make prepolymer;
C, preparation flame-retarded unsaturated polyester resin:
Dibasic alcohol with 1/2 mass parts of remainder, diprotic acid or dibasic acid anhydride, catalyzer, the stopper Hybrid Heating of silicon-series five-retardant and 1/2 mass parts is warmed up to 140～150 ℃, be incubated 0.5～1 hour, progressively be warmed up to 200～205 ℃ with 6～8 hours, be incubated 2～4 hours, add again the prepolymer that step b makes, heated to gradually 200～205 ℃ with 2～3 hours, begin decompression vacuum pumping 200～205 ℃ of lower reactions after 1～2 hour, make reactor vacuum tightness reach-0.093～-0.09MPa, be reaction end until acid number drops to 30～40mgKOH/g, cool to 100～120 ℃, the stopper and the mixing diluents that add 1/2 remaining mass parts are even, namely make response type halogen-free flameproof unsaturated polyester resin;
In above-described embodiment 21-30, described dibasic alcohol is two or more the mixture in ethylene glycol, 1,2-PD, neopentyl glycol, Diethylene Glycol, the dipropylene glycol;
Described dibasic alcohol is the mixture of 1,2-PD and ethylene glycol preferably, and the quality proportioning of 1,2-PD and ethylene glycol is 1:0.25～0.62.
In above-described embodiment 21-30, described diprotic acid or dibasic acid anhydride are two or more the mixture in fumaric acid, MALEIC ANHYDRIDE, Tetra hydro Phthalic anhydride, m-phthalic acid, the hexanodioic acid;
Described diprotic acid or dibasic acid anhydride are preferably the mixture of unsaturated dibasic acid or acid anhydrides and monounsaturated dicarboxylic acid or acid anhydrides, and unsaturated dibasic acid or acid anhydrides and monounsaturated dicarboxylic acid or acid anhydrides quality proportioning are 1:0～0.2; Described unsaturated dibasic acid acid or acid anhydrides are MALEIC ANHYDRIDE or fumaric acid; Described monounsaturated dicarboxylic acid or acid anhydrides are Tetra hydro Phthalic anhydride, m-phthalic acid or hexanodioic acid.
In above-described embodiment 21-30, described phosphorus flame retardant is one or more the mixture in 2-carboxyethyl phenyl Hypophosporous Acid, 50 (CEPPA), phenyl methylol Hypophosporous Acid, 50 (HMPPA), the benzenephosphonic acid benzenedio ester.
In above-described embodiment 21-30, described silicon-series five-retardant is one or more the mixture in hexichol dihydroxy silane, dihydroxy dimethylsilane, the phenyl methyl dihydroxy silane.
In above-described embodiment 21-30, described catalyzer is one or more the mixture in Dibutyltin oxide, sodium acetate, the two lauric acid butyl tin.
In above-described embodiment 21-30, described stopper is Resorcinol.
In above-described embodiment 21-30, described thinner is the mixture of vinylbenzene and trialkenyl methyl three isocyanuric acid fat (TAIC), vinylbenzene: the mass ratio of trialkenyl methyl three isocyanuric acid fat is 1:0.1～1, and the preferable quality proportioning is 1:0.23～1.
The response type halogen-free flameproof unsaturated polyester resin that adopts above-described embodiment 1～20 to obtain is applied in the moulding compound (SMC), common unsaturated polyester adopts the technical performance index of the SMC molding of same recipe preparation to compare on the prepared SMC molding sample of prepared response type halogen-free flameproof unsaturated polyester resin and the present market, its mechanical property is slightly high, and the oxygen index lifting is larger, has improved preferably the flame retardant properties of molding product.Its gordian technique performance index contrast such as following table:
In above-described embodiment: the processing parameter of each step and numerical value etc. are scope, and any point is all applicable.
The not concrete same prior art of technology contents of narrating in content of the present invention and above-described embodiment.
The invention is not restricted to above-described embodiment, content of the present invention is described all can implement and have described good result.
Claims (4)
1. the synthetic method of a response type halogen-free flameproof unsaturated polyester resin is characterized in that may further comprise the steps:
A, batching:
Raw material composition and mass ratio by dibasic alcohol 20～30 mass parts, diprotic acid or dibasic acid anhydride 25～35 mass parts, phosphorus flame retardant 8～20 mass parts, silicon-series five-retardant 2～7 mass parts, catalyzer 0.02～0.05 mass parts, stopper 0.014～0.04 mass parts, thinner 30～40 mass parts are got each component raw material;
B, preparation prepolymer:
Dibasic alcohol 10～15 mass parts and phosphorus flame retardant 8～20 mass parts are mixed, after 140～160 ℃ of temperature are reacted 3～5 hours down, again-0.093～-cool to room temperature after reacting 2～4 hours under the 0.09MPa vacuum tightness, 160～180 ℃ of conditions, make prepolymer;
C, preparation flame-retarded unsaturated polyester resin:
Dibasic alcohol 10～15 mass parts with remainder, diprotic acid or dibasic acid anhydride 25～35 mass parts, catalyzer 0.02～0.05 mass parts, silicon-series five-retardant 2～7 mass parts and stopper 0.007～0.02 mass parts Hybrid Heating are warmed up to 140～150 ℃, be incubated 0.5～1 hour, progressively be warmed up to 200～205 ℃ with 6～8 hours, be incubated 2～4 hours, add again the prepolymer that step b makes, heated to gradually 200～205 ℃ with 2～3 hours, begin decompression vacuum pumping 200～205 ℃ of lower reactions after 1～2 hour, make reactor vacuum tightness reach-0.093～-0.09MPa, be reaction end until acid number drops to 30～40mgKOH/g, cool to 100～120 ℃, add remaining stopper 0.007～0.02 mass parts and thinner 30～40 mass parts and mix, namely make response type halogen-free flameproof unsaturated polyester resin;
Described dibasic alcohol is two or more the mixture in ethylene glycol, 1,2-PD, neopentyl glycol, Diethylene Glycol, the dipropylene glycol;
Described diprotic acid or dibasic acid anhydride are two or more the mixture in fumaric acid, MALEIC ANHYDRIDE, Tetra hydro Phthalic anhydride, m-phthalic acid, the hexanodioic acid;
Described phosphorus flame retardant is one or more the mixture in 2-carboxyethyl phenyl Hypophosporous Acid, 50, phenyl methylol Hypophosporous Acid, 50, the benzenephosphonic acid benzenedio ester;
Described silicon-series five-retardant is one or more the mixture in hexichol dihydroxy silane, dihydroxy dimethylsilane, the phenyl methyl dihydroxy silane;
Described catalyzer is one or more the mixture in Dibutyltin oxide, sodium acetate, the two lauric acid butyl tin;
Described stopper is Resorcinol;
Described thinner is the mixture of vinylbenzene and trialkenyl methyl three isocyanuric acid esters, vinylbenzene: the mass ratio of trialkenyl methyl three isocyanuric acid esters is 1:0.1～1.
2. press the synthetic method of the described response type halogen-free flameproof unsaturated polyester of claim 1 resin, it is characterized in that: described diprotic acid or dibasic acid anhydride are the mixtures of unsaturated dibasic acid or acid anhydrides and monounsaturated dicarboxylic acid or acid anhydrides, and unsaturated dibasic acid or acid anhydrides and monounsaturated dicarboxylic acid or acid anhydrides quality proportioning are 1:0～0.2; Described unsaturated dibasic acid or acid anhydrides are MALEIC ANHYDRIDE or fumaric acid; Described monounsaturated dicarboxylic acid or acid anhydrides are Tetra hydro Phthalic anhydride, m-phthalic acid or hexanodioic acid.
3. by the synthetic method of claim 1 or 2 described response type halogen-free flameproof unsaturated polyester resins, it is characterized in that: described dibasic alcohol is the mixture of 1,2-PD and ethylene glycol, and the quality proportioning of 1,2-PD and ethylene glycol is 1:0.25～0.62.
4. by the synthetic method of claim 1 or 2 described response type halogen-free flameproof unsaturated polyester resins, it is characterized in that: the quality proportioning of described thinner vinylbenzene and trialkenyl methyl three isocyanuric acid esters is 1:0.23～1.
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| CN102408556A (en) * | 2011-09-26 | 2012-04-11 | 四川东材科技集团股份有限公司 | Preparation method of reactive polyester melt-drip-resistant flame retardant |
| CN104558567A (en) * | 2013-10-11 | 2015-04-29 | 中国石油化工股份有限公司 | A preparing method of halogen-free flame-retardant PBT copolyester |
| CN104031211A (en) * | 2014-06-17 | 2014-09-10 | 常州天马集团有限公司（原建材二五三厂） | Halogen-free flame retardant gel coat resin and preparation method thereof |
| CN104311877B (en) * | 2014-08-29 | 2019-05-21 | 成都拓利科技股份有限公司 | A kind of response type nylon fire retardant and preparation method |
| CN111823349A (en) * | 2020-07-06 | 2020-10-27 | 福建省尤溪县百源木业有限公司 | Manufacturing process of fireproof door frame with high fire resistance |
| CN112538245B (en) * | 2020-12-04 | 2022-11-29 | 广东晨宝复合材料股份有限公司 | Daylighting tile resin and preparation method thereof |
| CN114045133A (en) * | 2021-11-24 | 2022-02-15 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | Preparation method of high-thermal-conductivity flame-retardant epoxy modified unsaturated resin pouring sealant |
| CN115466385B (en) * | 2022-10-31 | 2024-03-26 | 中化学科学技术研究有限公司 | Polyamide film, preparation method and electronic device |
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| US3060146A (en) * | 1958-07-08 | 1962-10-23 | Pittsburgh Plate Glass Co | Polyester of a dicarboxylic acid and a halogen-containing polyol and mixtures thereof with an ethylenic monomer |
| CN101508770A (en) * | 2009-03-17 | 2009-08-19 | 四川东材科技集团股份有限公司 | Method for preparing phosphor system halogen-free flame-proof copolymerization polyester |
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| JP3362217B2 (en) * | 1998-07-14 | 2003-01-07 | 大塚化学株式会社 | Flame retardant resin composition |
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| US3060146A (en) * | 1958-07-08 | 1962-10-23 | Pittsburgh Plate Glass Co | Polyester of a dicarboxylic acid and a halogen-containing polyol and mixtures thereof with an ethylenic monomer |
| CN101508770A (en) * | 2009-03-17 | 2009-08-19 | 四川东材科技集团股份有限公司 | Method for preparing phosphor system halogen-free flame-proof copolymerization polyester |
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| JP特开2000-26741A 2000.01.25 |
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