CN102181260B - Preparation method of halogen-free flame-retardant polyurethane (PU) sealant - Google Patents
Preparation method of halogen-free flame-retardant polyurethane (PU) sealant Download PDFInfo
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Abstract
The invention relates to a preparation method of a halogen-free flame-retardant polyurethane (PU) sealant. The preparation method comprises the following steps: dewatering and drying the following materials, namely a filler, a thixotropic agent, a halogen-free flame retardant, a flame-retardant synergist, a plasticizer, a light stabilizer and an antioxidant in vacuum; stirring a PU prepolymer and the materials for dispersion in a double planet mixer with a high-speed dispersion disk or a tri-roller grinder at the temperature of 30-50 DEG C for 2-5 hours under the condition that the vacuum degree is not less than 0.092Mpa; under normal pressure and protection of high-purity nitrogen, adding a catalyst A, a silane adhesion promoter and a water scavenger, and stirring for 0.1-1 hour for dispersion; and removing small molecules and stirring for 0.3-1 hour under the condition that the vacuum degree is not less than 0.092Mpa to finally obtain the halogen-free flame-retardant PU sealant. The halogen-free flame-retardant PU sealant effectively overcomes the disadvantages of the PU sealant such as big flame, fast burning speed, severe drippage and the like in the prior art on the premise of ensuring the original physical properties of the PU sealant, thus the PU sealant has the advantages of flame retardance, no drippage during the burning process, good adhesive property and the like.
Description
Technical field
The present invention relates to polyurethane sealant technical field, particularly relate to a kind of preparation method of halogen-free anti-inflaming polyurethane seal gum.
Background technology
Polyurethane sealant has good UV resistant, excellent bonding strength, resistant to chemical media, anti-pull, shrinking percentage, low temperature flexibility, the performance such as wear-resisting.Therefore, be widely used in the fields such as building, automobile and boats and ships.
When polyurethane sealant burns being subject to extraneous thermal source, have that flame is large, combustionvelocity is fast, drip the shortcomings such as serious.Along with the raising of people to the field such as house ornamentation, building awareness of safety, the flame retardant properties of polyurethane sealant more and more comes into one's own.
In prior art, for fire-retardant fire retardants such as adding inorganic hydroxide, red phosphorus, ammonium polyphosphate that adopt of polyurethane sealant more, but, inorganic hydroxide fire retardant, have that flame retarding efficiency is low, addition large, poor with resin matrix consistency, cause the shortcomings such as product density is large than great; Red phosphorus combustion inhibitor, although flame retarding efficiency is higher, color is darker, is used for some black goods, and moisture absorption, the abrasive material time has the hypertoxic gases such as phosphuret-(t)ed hydrogen when long and emits, and has the danger of blast; Ammonium polyphosphate flame retardant, although have advantages of that phosphorus content is high, nitrogen content is large, in actual application, the easy moisture absorption of ammonium polyphosphate and reunion, poor with resin compatible, easily from resin, separate out, have a strong impact on its flame retardant effect.For improving the existing problem of ammonium polyphosphate flame retardant, more people adopt and change the method that molecular structure carries out modification to form the poly-phosphate (as trimeric cyanamide polyphosphoric acid ammonium salt) of other type, coupling agent modified surface etc. to it, but the problem that these methods can not fundamentally change its easy moisture absorption, separate out.
Therefore, for existing problem in prior art, provide a kind of in guaranteeing seal gum physicals, there is the preparation method of the halogen-free anti-inflaming polyurethane seal gum of good flame retardant effect, particularly important.
Summary of the invention
The preparation method who the object of the invention is to avoid weak point of the prior art and provide a kind of halogen-free anti-inflaming polyurethane seal gum, adopt the prepared halogen-free anti-inflaming polyurethane seal gum of this preparation method, can effectively solve that large, the combustionvelocity of flame that polyurethane sealant exists is fast, drippage serious problems.
Object of the present invention is achieved through the following technical solutions:
The preparation method that a kind of halogen-free anti-inflaming polyurethane seal gum is provided, comprises the following steps:
Step 1, prepares raw material by following mass ratio;
Base polyurethane prepolymer for use as 10～45 ﹪
Halogen-free flame retardants 10～25 ﹪
Fire retarding synergist 0～10 ﹪
Softening agent 10～35 ﹪
Thixotropic agent 1～10 ﹪
Filler 5～30 ﹪
Photostabilizer 0.1～0.5 ﹪
Oxidation inhibitor 0.1～0.5 ﹪
Catalyst A 0.001～0.005 ﹪
Silicane adhesion promoter 0.5～3 ﹪
Moisture scavenger 0.1～1.5 ﹪;
Wherein, the preparation method of described base polyurethane prepolymer for use as comprises: the two functionality polyether glycols that are 1:0.1～1.5 by mass ratio and three-functionality-degree polyether glycol join in reactor and stir, and the temperature that regulates reactor is 80～100 ℃, be not less than in vacuum tightness under the condition of 0.092Mpa, 2～5h dewaters, be cooled to 60～80 ℃, after temperature-stable, in reactor, add the catalyst B that NCO/OH is 1.2～2.5 isocyanate curing agent and 0.001～0.005 ﹪ that accounts for said mixture total mass again, after reaction 2～4h, obtain base polyurethane prepolymer for use as,
Separately, said mixture total mass comprises the total mass of two functionality polyether glycols, three-functionality-degree polyether glycol and isocyanate curing agent;
Wherein, described catalyst B be in dibutyl tin laurate, stannous octoate, modification organotin catalysts any or several;
Step 2, will by above-mentioned formula ratio, base polyurethane prepolymer for use as and the dried filler of process vaccum dewatering, thixotropic agent, halogen-free flame retardants, fire retarding synergist, softening agent, photostabilizer and oxidation inhibitor, be not less than 0.092 Mpa in vacuum tightness, temperature is to carry out after dispersed with stirring 2～5h in the double-planet stirrer with high speed dispersion dish of 30～50 ℃ or three-roll grinder, under normal pressure and high pure nitrogen protection, add catalyst A, silicane adhesion promoter and moisture scavenger, dispersed with stirring 0.1～1h, be not less than under 0.092 Mpa in vacuum tightness, deviate from small molecules and be uniformly mixed 0.3～1h, obtain halogen-free anti-inflaming polyurethane seal gum,
Separately, the proportioning raw materials in above-mentioned steps one can also be following mass ratio:
Base polyurethane prepolymer for use as 20～45 ﹪
Halogen-free flame retardants 15～25 ﹪
Fire retarding synergist 5～10 ﹪
Softening agent 10～25 ﹪
Thixotropic agent 1～8 ﹪
Filler 5～25 ﹪
Photostabilizer 0.1～0.5 ﹪
Oxidation inhibitor 0.1～0.5 ﹪
Catalyst A 0.001～0.005 ﹪
Silicane adhesion promoter 0.5～3 ﹪
Moisture scavenger 0.1～1.5 ﹪.
In the technical program, described catalyst A be in two (dimethylaminoethyl) ether, dual-morpholinyl diethyl ether, N-Methylimidazole, triethylamine, methyldiethanolamine any or several.
In the technical program, described two functionality polyether glycols are that molecular weight is 2000～10000 Polyoxypropylene diol; Described three-functionality-degree polyether glycol is that molecular weight is 3000～8000 polyoxytrimethylene trivalent alcohol.
In the technical program, described isocyanate curing agent is tolylene diisocyanate, ditan-4, any in 4 '-vulcabond, thick diphenylmethanediisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and dicyclohexyl methane diisocyanate.
In the technical program, described halogen-free flame retardants is any or two kinds in the coated micro encapsulation ammonium polyphosphate of phenol aldehyde type epoxy resin and the coated micro encapsulation melamine polyphosphate of phenol aldehyde type epoxy resin.
Separately, the preparation method of the coated micro encapsulation ammonium polyphosphate of phenol aldehyde type epoxy resin, comprising: 2～4g phenol aldehyde type epoxy resin and 0.5～1.5g fat polyamine or aromatic multi-amine solidifying agent are placed in to 60～80mL ethanol, and dispersed with stirring forms mixture A; Under the condition stirring, in mixture A, add ammonium polyphosphate flame retardant (APP) and sodium lauryl sulphate, stir after 25～35 minutes, be warming up to 60～110 ℃, and react 2～7h at this temperature, obtain mixture B; Wherein, the add-on of APP is 8～25 times of phenol aldehyde type epoxy resin quality, and the add-on of sodium lauryl sulphate is 0.1～4 ﹪ of phenol aldehyde type epoxy resin and fat polyamine or aromatic multi-amine solidifying agent total mass; By mixture B suction filtration, with absolute ethanol washing number time, at 100～120 ℃, be dried 5～12h, to obtain final product.Wherein, fat polyamine or aromatic multi-amine solidifying agent can adopt quadrol or mphenylenediamine.
Separately, the preparation method of the coated micro encapsulation melamine polyphosphate of phenol aldehyde type epoxy resin, comprise: 2～4g phenol aldehyde type epoxy resin and 0.5～1.5g fat polyamine or aromatic multi-amine solidifying agent are placed in to 60～80mL methyl alcohol, and dispersed with stirring forms mixture A; Under the condition stirring, in mixture A, add fire retardant melamine polyphosphate and sodium lauryl sulphate, stir after 25～35 minutes, be warming up to 60～110 ℃, and react 2～7h at this temperature, obtain mixture B; Wherein, the add-on of APP is 8～25 times of phenol aldehyde type epoxy resin quality, and the add-on of sodium lauryl sulphate is 0.1～4 ﹪ of phenol aldehyde type epoxy resin and fat polyamine or aromatic multi-amine solidifying agent total mass; By mixture B suction filtration, with anhydrous methanol washing several times, at 100～120 ℃, be dried 5～12h, to obtain final product.Wherein, fat polyamine or aromatic multi-amine solidifying agent can adopt quadrol or mphenylenediamine.
In the technical program, described fire retarding synergist be in talcum powder, zinc borate, antimonous oxide, antimony pentaoxide, organic modification montmonrillonite, zinc oxide, mica powder and silicon powder any or several.
In the technical program, described softening agent be in o-phthalic acid dibutyl ester, Dinonylphthalate, Di Iso Decyl Phthalate, hexanodioic acid dibutyl ester and didecyl adipate any or several.
In the technical program, described thixotropic agent be in nm-class active calcium carbonate, hydrogenated castor oil, nano fumed silica, organobentonite and diatomite any or several.
In the technical program, described filler be particle diameter be 2000～8000 object coarse whitings, particle diameter be 1000～5000 kaolin and particle diameter be in 1000～5000 active fine particle calcium carbonate any or several.
In the technical program, the ultraviolet absorbers that described photostabilizer is benzotriazole category or the UV light stabilizing agent of hindered amines; The ultraviolet absorbers of described benzotriazole category is Tinuvin213 or UV-320; The UV light stabilizing agent of described hindered amines is (2,2,6,6-tetramethyl piperidine) sebate or 4-benzoyloxy-2,2,6,6-tetramethyl piperidine.
In the technical program, described oxidation inhibitor be in Irgastab PUR68, antioxidant 1010 and Irganox 5057 any or several; Described silicane adhesion promoter be in γ mercaptopropyitrimethoxy silane, γ-sulfydryl propyl-triethoxysilicane, β-(3,4-epoxy group(ing) hexyl) ethyl trimethoxy silane, γ-aminopropyl triethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-methacryloxypropyl trimethoxy silane, γ-aminopropyltrimethoxysilane and γ-glycidyl ether oxygen base propyl trimethoxy silicane any or several; Described moisture scavenger be easily hydrolyzed reaction silane coupling agent, tricarboxylic acid trimethyl and oxazole alkanes moisture scavenger in any or several.
Beneficial effect of the present invention: the halogen-free anti-inflaming polyurethane seal gum that the present invention adopts halogen-free flame retardants to prepare, in guaranteeing the original physicals of polyurethane sealant, effectively overcome that the flame that polyurethane sealant of the prior art exists is large, combustionvelocity fast, drip the shortcomings such as serious, the advantage such as while thering is difficult combustion, burning, do not drip, cementability is good, can be widely used in the field such as vehicle, building.Compared with prior art, further have the following advantages: (1) specifically selects the coated micro encapsulation ammonium polyphosphate of phenol aldehyde type epoxy resin or the coated micro encapsulation melamine polyphosphate of phenol aldehyde type epoxy resin as main flame retardant, effectively solve the easy moisture absorption of ammonium polyphosphate, reunion, poor with resin compatible, easily the shortcoming such as from resin, separate out in, by having in the phenol aldehyde type epoxy resin introducing system of charcoal effect, effectively improve flame retardant effect; (2) select the coated micro encapsulation melamine polyphosphate of the coated micro encapsulation ammonium polyphosphate of phenol aldehyde type epoxy resin or phenol aldehyde type epoxy resin, solved and processed the existing residual formaldehyde of ammonium polyphosphate as melamine-formaldehyde micro encapsulation and be difficult to remove clean follow-up pollution problem; (3) select suitable fire retarding synergist, in guaranteeing and improving Flame Retardancy energy, the total addition level of fire retarding synergist is reduced, effectively alleviated the destruction of additional powder to resin system performance.The prepared halogen-free anti-inflaming polyurethane seal gum of the present invention especially has good adhesiveproperties to glass, marble, cement etc., is applicable to the field such as vehicle, building.
Embodiment
The invention will be further described with the following Examples:
It should be noted that, the testing standard of flame retardant properties is according to GB/T2408-1996, the testing standard of outward appearance is according to JC/T482-2003, the testing standard of surface drying time is according to JC/T482-2003, the testing standard of sag is according to JC/T482-2003, and extrudability testing standard is according to JC/T482-2003, and the testing standard of 23 ℃ of orientation stretching modulus is according to JC/T482-2003, the testing standard of directed cementability is according to JC/T482-2003, and the testing standard of mass loss rate is according to JC/T482-2003.
comparative example
A preparation method for halogen-free anti-inflaming polyurethane seal gum, comprises the following steps:
Step 1, prepares raw material by following quality;
Base polyurethane prepolymer for use as 300g
Ammonium polyphosphate 250g
Dioctyl phthalate (DOP) 250g
Nano fumed silica 20g
2000 order coarse whiting 171g
UV- 320 0.5g
Irgastab PUR68 0.5g
Two (dimethylaminoethyl) ether 0.02g
γ-aminopropyl triethoxysilane 5g
Tricarboxylic acid trimethyl 3g;
Step 2, by base polyurethane prepolymer for use as 300g and the dried 2000 order coarse whiting 171g of process vaccum dewatering, nano fumed silica 20g, not coated ammonium polyphosphate 250g, dioctyl phthalate (DOP) 250g, UV-320 0.5g, Irgastab PUR68 0.5g, be 0.095Mpa in vacuum tightness, temperature is that the double-planet stirrer with high speed dispersion dish of 35 ℃ carries out after dispersed with stirring 2h, under normal pressure and high pure nitrogen protection, add two (dimethylaminoethyl) ether 0.02g, γ-aminopropyl triethoxysilane 5g and tricarboxylic acid trimethyl 3g, dispersed with stirring 0.5h, under the condition that is 0.095Mpa in vacuum tightness, deviate from small molecules and be uniformly mixed 0.5h, obtain halogen-free anti-inflaming polyurethane seal gum, its performance sees the following form 1.
The preparation method of the base polyurethane prepolymer for use as in comparative example: the polyether glycol 400g that adds molecular weight and be the polyether glycol 1000g of 2000 liang of functionality and molecular weight and be 5000 three-functionality-degrees stirs in reactor, and the temperature that regulates reactor is 90 ℃, after mixing, be under 0.095Mpa in vacuum tightness, 3h dewaters, be cooled to 65 ℃, after temperature-stable, add 282g ditan-4,4 '-vulcabond, and adding the dibutyl tin laurate of 0.03364g, reaction 3h, obtains base polyurethane prepolymer for use as.
embodiment 1
A preparation method for halogen-free anti-inflaming polyurethane seal gum, comprises the following steps:
Step 1, prepare raw material by following quality:
Base polyurethane prepolymer for use as 300g
Phenol aldehyde type epoxy resin is coated micro encapsulation ammonium polyphosphate 210g
Zinc borate 20g
Dioctyl phthalate (DOP) 250g
Nano fumed silica 20g
2000 order coarse whiting 191g
UV- 320 0.5g
Irgastab PUR68 0.5g
Two (dimethylaminoethyl) ether 0.02g
γ-aminopropyl triethoxysilane 5g
Tricarboxylic acid trimethyl 3g;
Step 2, will by above-mentioned formula ratio, base polyurethane prepolymer for use as 300g and the dried 2000 order coarse whiting 191g of process vaccum dewatering, nano fumed silica 20g, phenol aldehyde type epoxy resin is coated micro encapsulation ammonium polyphosphate 210g, zinc borate 20g, dioctyl phthalate (DOP) 250g, UV-320 0.5g, Irgastab PUR68 0.5g, be 0.095Mpa in vacuum tightness, temperature is that the double-planet stirrer with high speed dispersion dish of 35 ℃ carries out after dispersed with stirring 2h, under normal pressure and high pure nitrogen protection, add two (dimethylaminoethyl) ether 0.02g, γ-aminopropyl triethoxysilane 5g and tricarboxylic acid trimethyl 3g, dispersed with stirring 0.5h, be under 0.095Mpa in vacuum tightness, deviate from small molecules and be uniformly mixed 0.5h, obtain halogen-free anti-inflaming polyurethane seal gum, its performance sees the following form 1.
The preparation method of the base polyurethane prepolymer for use as in the present embodiment comprises: the polyether glycol 400g that adds molecular weight and be the polyether glycol 1000g of 2000 liang of functionality and molecular weight and be 5000 three-functionality-degrees joins in reactor and stirs, and the temperature that regulates reactor is 90 ℃, after mixing, under the condition that is 0.095Mpa in vacuum tightness, 3h dewaters, be cooled to 65 ℃, after temperature-stable, in reactor, add 282g ditan-4 again, 4 '-vulcabond, and add the dibutyl tin laurate of 0.03364g, after reaction 3h, obtain base polyurethane prepolymer for use as.
embodiment 2
A preparation method for halogen-free anti-inflaming polyurethane seal gum, comprises the following steps:
Step 1, prepares raw material by following quality;
Base polyurethane prepolymer for use as 450g
Phenol aldehyde type epoxy resin is coated micro encapsulation ammonium polyphosphate 180g
Talcum powder 30g
Dinonylphthalate 200g
Nm-class active calcium carbonate 50g
3000 order kaolin 74.4g
UV -320 0.3g
Irganox 5057 0.3g
N-Methylimidazole 0.03g
γ-methacryloxypropyl trimethoxy silane 10g
Tricarboxylic acid trimethyl 5g;
Step 2, will by above-mentioned formula ratio, base polyurethane prepolymer for use as 450g and the dried 3000 order kaolin 74.4g of process vaccum dewatering, nm-class active calcium carbonate 50g, phenol aldehyde type epoxy resin is coated micro encapsulation ammonium polyphosphate 180g, talcum powder 30g, Dinonylphthalate 200g, UV-320 0.3g, Irganox 5057 0.3g, be 0.097Mpa in vacuum tightness, temperature is that the double-planet stirrer with high speed dispersion dish of 40 ℃ carries out after dispersed with stirring 2h, under the protection of normal pressure and high pure nitrogen, add N-Methylimidazole 0.03g, γ-methacryloxypropyl trimethoxy silane 10g and tricarboxylic acid trimethyl 5g, dispersed with stirring 0.6h, be under 0.095Mpa in vacuum tightness, deviate from small molecules and be uniformly mixed 0.7h, obtain halogen-free anti-inflaming polyurethane seal gum, its performance sees the following form 1.
The preparation method of the base polyurethane prepolymer for use as in the present embodiment comprises: the polyether glycol 250g that adds molecular weight and be the polyether glycol 750g of 5000 liang of functionality and molecular weight and be 6000 three-functionality-degrees stirs in reactor, and the temperature that regulates reactor is 100 ℃, after mixing, under the condition that is 0.097Mpa in vacuum tightness, 2.5h dewaters, be cooled to 70 ℃, after homo(io)thermism, add 112.5g ditan-4,4 '-vulcabond, and add 0.03338g dibutyl tin laurate, after reaction 2h, obtain base polyurethane prepolymer for use as.
embodiment 3
A preparation method for halogen-free anti-inflaming polyurethane seal gum, comprises the following steps:
Step 1, prepares raw material by following mass ratio;
Base polyurethane prepolymer for use as 350g
Phenol aldehyde type epoxy resin is coated micro encapsulation ammonium polyphosphate 160g
Antimonous oxide 20g
Hexanodioic acid dibutyl ester 250g
Hydrogenated castor oil 50g
1000 order activated Calcium carbonate 154.5g
UV -320 0.2g
Irganox 5057 0.3g
Methyldiethanolamine 0.03g
β-(3,4-epoxy group(ing) hexyl) ethyl trimethoxy silane 10g
Oxazole alkanes moisture scavenger 5g;
Step 2, will by above-mentioned formula ratio, base polyurethane prepolymer for use as 350g and the dried 1000 order activated Calcium carbonate 154.5g of process vaccum dewatering, hydrogenated castor oil 50g, phenol aldehyde type epoxy resin is coated micro encapsulation ammonium polyphosphate 160g, antimonous oxide 20g, hexanodioic acid dibutyl ester 250g, UV-320 0.2g, Irganox 5057 0.3g, be 0.097Mpa in vacuum tightness, temperature is that the double-planet stirrer with high speed dispersion dish of 45 ℃ carries out after dispersed with stirring 2h, under normal pressure and high pure nitrogen protection, add methyldiethanolamine 0.03g, β-(3, 4-epoxy group(ing) hexyl) ethyl trimethoxy silane 10g and oxazole alkanes moisture scavenger 5g, dispersed with stirring 0.6h, be under 0.095Mpa in vacuum tightness, deviating from small molecules is uniformly mixed after 0.7h, obtain halogen-free anti-inflaming polyurethane seal gum, its performance sees the following form 1.
The preparation method of the base polyurethane prepolymer for use as in the present embodiment comprises: the polyether glycol 200g that adds molecular weight and be the polyether glycol 200g of 2000 liang of functionality and molecular weight and be 8000 three-functionality-degrees stirs in reactor, and the temperature that regulates reactor is 95 ℃, after mixing, under the condition that is 0.095Mpa in vacuum tightness, 3.5h dewaters, be cooled to 60 ℃, after temperature-stable, add 55g tolylene diisocyanate, and add the stannous octoate of 0.0182g, after reaction 3h, obtain base polyurethane prepolymer for use as.
embodiment 4
A preparation method for halogen-free anti-inflaming polyurethane seal gum, comprises the following steps:
Step 1, prepares raw material by following mass ratio;
Base polyurethane prepolymer for use as 250g
Phenol aldehyde type epoxy resin is coated micro encapsulation melamine polyphosphate 140g
Antimony pentaoxide 40g
Didecyl adipate 300g
Nano silicon 15g
5000 order activated Calcium carbonate 242.5g
UV- 320 0.3g
Irganox 5057 0.2g
Triethylamine 0.03g
γ-glycidyl ether oxygen base propyl trimethoxy silicane 6g
Oxazole alkanes moisture scavenger 6g;
Step 2, will by above-mentioned formula ratio, base polyurethane prepolymer for use as 250g and the dried 5000 order activated Calcium carbonate 242.5g of process vaccum dewatering, nano silicon 15g, phenol aldehyde type epoxy resin is coated micro encapsulation melamine polyphosphate 140g, antimony pentaoxide 40g, didecyl adipate 300g, UV-320 0.3g, Irganox 5057 0.2g, be 0.094Mpa in vacuum tightness, temperature is that the double-planet stirrer with high speed dispersion dish of 50 ℃ carries out after dispersed with stirring 2.5h, under normal pressure and high pure nitrogen protection, add triethylamine 0.03g, γ-glycidyl ether oxygen base propyl trimethoxy silicane 6g and oxazole alkanes moisture scavenger 6g, dispersed with stirring 1.0h, be under 0.094Mpa in vacuum tightness, deviate from small molecules and be uniformly mixed 1.0h, obtain halogen-free anti-inflaming polyurethane seal gum, its performance sees the following form 1.
The preparation method of the base polyurethane prepolymer for use as in the present embodiment comprises: the polyether glycol 240g that adds molecular weight and be the polyether glycol 200g of 3000 liang of functionality and molecular weight and be 5000 three-functionality-degrees stirs in reactor, and the temperature that regulates reactor is 92 ℃, after mixing, under the condition that is 0.094Mpa in vacuum tightness, 4.5h dewaters, be cooled to 62 ℃, after temperature-stable, add 62g ditan-4,4 '-vulcabond, and add stannous octoate 0.0251g, after reaction 3.5h, obtain base polyurethane prepolymer for use as.
embodiment 5
A preparation method for halogen-free anti-inflaming polyurethane seal gum, comprises the following steps:
Step 1, prepares raw material by following mass ratio;
Base polyurethane prepolymer for use as 210g
Phenol aldehyde type epoxy resin is coated microencapsulation melamine polyphosphate 190g
Organic modification montmonrillonite 30g
Dinonylphthalate 200g
Nano-calcium carbonate 100g
5000 order kaolin 249g
UV- 320 0.5g
Irganox 5057 0.5g
Dual-morpholinyl diethyl ether 0.02g
γ-sulfydryl propyl-triethoxysilicane 12g
Oxazole alkanes moisture scavenger 8g;
Step 2, will by above-mentioned formula ratio, base polyurethane prepolymer for use as 210g and the dried 5000 order kaolin 249g of process vaccum dewatering, nano-calcium carbonate 100g, phenol aldehyde type epoxy resin is coated microencapsulation melamine polyphosphate 190g, organic modification montmonrillonite 30g, Dinonylphthalate 200g, UV-320 0.5g, Irganox 5057 0.5g, be 0.098Mpa in vacuum tightness, temperature is to carry out after grinding distribution 4.0h in the three-roll grinder of 45 ℃, in normal pressure and high pure nitrogen protection, add dual-morpholinyl diethyl ether 0.02g, γ-sulfydryl propyl-triethoxysilicane 12g and oxazole alkanes moisture scavenger 8g, grinding distribution 0.8h, it is 0.098 time in vacuum tightness, deviate from small molecules and be uniformly mixed 0.8h, obtain halogen-free anti-inflaming polyurethane seal gum, its performance sees the following form 1.
The preparation method of the base polyurethane prepolymer for use as in the present embodiment comprises: the polyether glycol 160g that adds molecular weight and be the polyether glycol 200g of 4000 liang of functionality and molecular weight and be 5000 three-functionality-degrees stirs in reactor, and the temperature that regulates reactor is 85 ℃, after mixing, under the condition that is 0.096Mpa in vacuum tightness, 3.5h dewaters, be cooled to 67 ℃, after temperature-stable, add 44.4g ditan-4,4 '-vulcabond, and adding stannous octoate 0.00809g, reaction 2.5h, obtains base polyurethane prepolymer for use as.
The contrast properties of table 1 comparative example and embodiment
| Test event | Comparative example | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Flame retardant properties | FV-0 | FV-0 | FV-0 | FV-0 | FV-0 | FV-0 |
| Outward appearance (range estimation) | Finer and smoother, there is a small amount of particle | Exquisiteness, gel-free, bubble | Exquisiteness, gel-free, bubble | Exquisiteness, gel-free, bubble | Exquisiteness, gel-free, bubble | Exquisiteness, gel-free, bubble |
| Surface drying time (h) | 3.5 | 2.5 | 2 | 3 | 2 | 1 |
| Sag (mm) | 0 | 0 | 0 | 0 | 0 | 0 |
| Extrudability (ml/min) | 180 | 240 | 270 | 250 | 210 | 190 |
| 23 ℃ of orientation stretching modulus (MPa) | 0.93 | 1.25 | 1.41 | 1.37 | 1.18 | 1.04 |
| Directed cementability | Without destroying | Without destroying | Without destroying | Without destroying | Without destroying | Without destroying |
| Mass loss rate | 1.8 | 1.3 | 1.6 | 1.1 | 1.2 | 1.4 |
Finally should be noted that; above embodiment is only in order to illustrate technical scheme of the present invention; but not limiting the scope of the invention; although the present invention has been done to explain with reference to preferred embodiment; those of ordinary skill in the art is to be understood that; can modify or be equal to replacement technical scheme of the present invention, and not depart from essence and the scope of technical solution of the present invention.
Claims (8)
1. a preparation method for halogen-free anti-inflaming polyurethane seal gum, is characterized in that, comprises the following steps:
Step 1, prepares raw material by following mass ratio;
Base polyurethane prepolymer for use as 10～45 ﹪
Halogen-free flame retardants 10～25 ﹪
Fire retarding synergist
～10 ﹪
Softening agent 10～35 ﹪
Thixotropic agent 1～10 ﹪
Filler 5～30 ﹪
Photostabilizer 0.1～0.5 ﹪
Oxidation inhibitor 0.1～0.5 ﹪
Catalyst A 0.001～0.005 ﹪
Silicane adhesion promoter 0.5～3 ﹪
Moisture scavenger 0.1～1.5 ﹪;
Wherein, the preparation method of described base polyurethane prepolymer for use as comprises: the two functionality polyether glycols that are 1:0.1～1.5 by mass ratio and three-functionality-degree polyether glycol join in reactor and stir, and the temperature that regulates reactor is 80～100 ℃, be not less than in vacuum tightness under the condition of 0.092Mpa, 2～5h dewaters, be cooled to 60～80 ℃, after temperature-stable, in reactor, add the catalyst B that NCO/OH is 1.2～2.5 isocyanate curing agent and 0.001～0.005 ﹪ that accounts for said mixture total mass again, after reaction 2～4h, obtain base polyurethane prepolymer for use as,
Wherein, described catalyst B be in dibutyl tin laurate, stannous octoate, modification organotin catalysts any or several;
Step 2, will by above-mentioned formula ratio, base polyurethane prepolymer for use as and the dried filler of process vaccum dewatering, thixotropic agent, halogen-free flame retardants, fire retarding synergist, softening agent, photostabilizer and oxidation inhibitor, be not less than 0.092 Mpa in vacuum tightness, temperature is to carry out after dispersed with stirring 2～5h in the double-planet stirrer with high speed dispersion dish of 30～50 ℃ or three-roll grinder, under normal pressure and high pure nitrogen protection, add catalyst A, silicane adhesion promoter and moisture scavenger, dispersed with stirring 0.1～1h, be not less than under 0.092 Mpa in vacuum tightness, deviate from small molecules and be uniformly mixed 0.3～1h, obtain halogen-free anti-inflaming polyurethane seal gum,
Wherein, described halogen-free flame retardants is any or two kinds in the coated micro encapsulation ammonium polyphosphate of phenol aldehyde type epoxy resin and the coated micro encapsulation melamine polyphosphate of phenol aldehyde type epoxy resin;
Wherein, described fire retarding synergist be in talcum powder, zinc borate, antimonous oxide, antimony pentaoxide, organic modification montmonrillonite, zinc oxide, mica powder and silicon powder any or several;
Wherein, described catalyst A be in two (dimethylaminoethyl) ether, dual-morpholinyl diethyl ether, N-Methylimidazole, triethylamine, methyldiethanolamine any or several.
2. the preparation method of a kind of halogen-free anti-inflaming polyurethane seal gum according to claim 1, is characterized in that: described two functionality polyether glycols are that molecular weight is 2000～10000 Polyoxypropylene diol; Described three-functionality-degree polyether glycol is that molecular weight is 3000～8000 polyoxytrimethylene trivalent alcohol.
3. the preparation method of a kind of halogen-free anti-inflaming polyurethane seal gum according to claim 1, it is characterized in that: described isocyanate curing agent is tolylene diisocyanate, ditan-4 any in 4 '-vulcabond, thick diphenylmethanediisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and dicyclohexyl methane diisocyanate.
4. the preparation method of a kind of halogen-free anti-inflaming polyurethane seal gum according to claim 1, is characterized in that: described softening agent be in o-phthalic acid dibutyl ester, Dinonylphthalate, Di Iso Decyl Phthalate, hexanodioic acid dibutyl ester and didecyl adipate any or several.
5. the preparation method of a kind of halogen-free anti-inflaming polyurethane seal gum according to claim 1, is characterized in that: described thixotropic agent be in nm-class active calcium carbonate, hydrogenated castor oil, nano fumed silica, organobentonite and diatomite any or several.
6. the preparation method of a kind of halogen-free anti-inflaming polyurethane seal gum according to claim 1, is characterized in that: described filler be particle diameter be 2000～8000 object coarse whitings, particle diameter be 1000～5000 object kaolin and particle diameter be in the active fine particle calcium carbonates of 1000～5000 objects any or several.
7. the preparation method of a kind of halogen-free anti-inflaming polyurethane seal gum according to claim 1, is characterized in that: the ultraviolet absorbers that described photostabilizer is benzotriazole category or the UV light stabilizing agent of hindered amines; The ultraviolet absorbers of described benzotriazole category is Tinuvin213 or UV-320; The UV light stabilizing agent of described hindered amines is (2,2,6,6-tetramethyl piperidine) sebate or 4-benzoyloxy-2,2,6,6-tetramethyl piperidine.
8. the preparation method of a kind of halogen-free anti-inflaming polyurethane seal gum according to claim 1, is characterized in that: described oxidation inhibitor be in Irgastab PUR68, antioxidant 1010 and Irganox 5057 any or several; Described silicane adhesion promoter be in γ mercaptopropyitrimethoxy silane, γ-sulfydryl propyl-triethoxysilicane, β-(3,4-epoxy group(ing) hexyl) ethyl trimethoxy silane, γ-aminopropyl triethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-methacryloxypropyl trimethoxy silane, γ-aminopropyltrimethoxysilane and γ-glycidyl ether oxygen base propyl trimethoxy silicane any or several; Described moisture scavenger be easily hydrolyzed reaction silane coupling agent, tricarboxylic acid trimethyl and oxazole alkanes moisture scavenger in any or several.
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Address after: 523000 Guangdong city of Dongguan province Guangdong Town Village nine Pu Saida sealing adhesive Co. Ltd Patentee after: GUANGDONG PUSTAR SEALING ADHESIVE CO., LTD. Address before: 523000 Guangdong city of Dongguan Province town third Jinlong Industrial Zone Dongguan pustar sealing adhesive Co. Ltd Patentee before: Dongguan Pustar Adhesives & Sealants Co., Ltd. |