CN103396526A - Production method of solidifiable transparent anti-yellowing polyurethane prepolymer - Google Patents
Production method of solidifiable transparent anti-yellowing polyurethane prepolymer Download PDFInfo
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- CN103396526A CN103396526A CN2013102783798A CN201310278379A CN103396526A CN 103396526 A CN103396526 A CN 103396526A CN 2013102783798 A CN2013102783798 A CN 2013102783798A CN 201310278379 A CN201310278379 A CN 201310278379A CN 103396526 A CN103396526 A CN 103396526A
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- castor oil
- polyvalent alcohol
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- aliphatic isocyanates
- alcohol
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 238000004383 yellowing Methods 0.000 title claims abstract description 21
- 229920001730 Moisture cure polyurethane Polymers 0.000 title claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 31
- 239000004359 castor oil Substances 0.000 claims abstract description 30
- 235000019438 castor oil Nutrition 0.000 claims abstract description 30
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims abstract description 30
- -1 aliphatic isocyanate Chemical class 0.000 claims abstract description 29
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 28
- 229920000570 polyether Polymers 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000012948 isocyanate Substances 0.000 claims abstract description 25
- 238000007599 discharging Methods 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 72
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 39
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 36
- 150000005846 sugar alcohols Polymers 0.000 claims description 27
- 229920000728 polyester Polymers 0.000 claims description 25
- 229920001577 copolymer Polymers 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- 229920001634 Copolyester Polymers 0.000 claims description 11
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000009413 insulation Methods 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 6
- 239000012467 final product Substances 0.000 claims description 6
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 6
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 claims description 5
- 230000006837 decompression Effects 0.000 claims description 5
- 229960005082 etohexadiol Drugs 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000006068 polycondensation reaction Methods 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 2
- 239000003292 glue Substances 0.000 abstract description 14
- 229920000642 polymer Polymers 0.000 abstract description 9
- 239000002904 solvent Substances 0.000 abstract description 5
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 239000005056 polyisocyanate Substances 0.000 abstract description 3
- 229920001228 polyisocyanate Polymers 0.000 abstract description 3
- 150000003077 polyols Chemical class 0.000 abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 2
- 229920005906 polyester polyol Polymers 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 229920005862 polyol Polymers 0.000 abstract 2
- 230000009965 odorless effect Effects 0.000 abstract 1
- 238000004321 preservation Methods 0.000 abstract 1
- 239000012974 tin catalyst Substances 0.000 abstract 1
- 238000004026 adhesive bonding Methods 0.000 description 6
- 238000004448 titration Methods 0.000 description 4
- 239000012780 transparent material Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 3
- 239000012943 hotmelt Substances 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- OJRJDENLRJHEJO-UHFFFAOYSA-N 2,4-diethylpentane-1,5-diol Chemical compound CCC(CO)CC(CC)CO OJRJDENLRJHEJO-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000000873 masking effect Effects 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 230000009967 tasteless effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004831 Hot glue Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- SVTBMSDMJJWYQN-UHFFFAOYSA-N hexylene glycol Natural products CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 1
- 150000002527 isonitriles Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to the field of polymer chemical industries, and particularly discloses a production method of solidifiable transparent anti-yellowing polyurethane prepolymer which does not contain a solvent, is non-toxic, odorless and hardly yellows after being illuminated with substantially reduced glue temperature. The production method comprises the following steps of: adding polyether polyol, castor oil polyol and liquid copolymerization polyester polyol to a reaction kettle, stirring for 2 hours, then adding aliphatic isocyanate, reducing temperature to 80 DEG C, carrying out heat preservation and reacting for 2.5 hours, then adding an organic tin catalyst, continuously reacting for 1 hour, reducing temperature to 60 DEG C, discharging and storing in an airtight manner. After being cured, the prepolymer obtained by the production method of the solidifiable transparent anti-yellowing polyurethane prepolymer is completely transparent. As a polyisocyanate component containing a benzene ring component is not used, after the glue is applied, an illuminated glue layer hardly yellows. Meanwhile, polyfunctionality components such as castor oil derivatives are used, so that the mechanical property of the prepolymer is improved.
Description
Technical field
The present invention relates to the macromolecule chemical industry field, especially a kind of production method of curable transparent yellowing-resistant base polyurethane prepolymer for use as.
Background technology
The adhesive solvent pollution problem is puzzlement glue production and a difficult problem of using enterprise always, and adopting solvent-free water-base resin or hot-melt resin is the prior development direction of present adhesive area.Moisture-curable polyurethane glue is because curing speed soon, does not use solvent, solidifies the rear high industries such as Furniture manufacture, automotive trim manufacture, adhesive bookbinding that are widely used in of bond strength.Moisture-curable polyurethane glue typically uses crystal type polyester and the synthetic polyurethane prepolymer that contains terminal isocyanate group of aromatic polyisocyanate, after applying glue, in the several seconds, relies on the physical crystal of polyester to produce initial grab; Along with open assembly time extends, isocyanate groups absorbs in air and the moisture on bur surface completes chain extending reaction, namely solidifies afterwards.But this type of glue is generally opaque or translucent solid, or by transparent, becomes opaquely after solidifying, and to transparent material is bonding, can produce inaesthetic glue trace; And light is to the transmission of transparent material, and the gluing place is xanthochromia gradually.Especially when bonding transparent material was used for decoration and packaging field, glue trace and xanthochromia were unacceptable.
Present manufacturing enterprise uses the bonding transparent material of hot melt adhesive that contains the TPO composition usually, can obtain the good transparency and anti-yellowing property, but the gluing temperature requirement of such glue easily causes the thermal change type of bonded material more than 140～180 ℃.Such tackiness agent softening temperature is 80 ℃ of left and right, also poor to base material sticking power simultaneously, is difficult to meet the requirements at the higher level of bonding strength, thermotolerance and weather resistance.
Summary of the invention
The objective of the invention is provides a kind of glue temperature significantly to reduce for the deficiency that solves above-mentioned technology, and performed polymer does not contain after solvent, nontoxic, tasteless and illumination the production method that is difficult for the curable transparent yellowing-resistant base polyurethane prepolymer for use as of xanthochromia.
the production method of the designed curable transparent yellowing-resistant base polyurethane prepolymer for use as of the present invention in order to achieve the above object, to with vacuum dewatering plant, thermometer, in the reactor of agitator and condensing works, drop into polyether glycol, castor oil polyhydric alcohol and liquid copolymeric polyester polyvalent alcohol, in vacuum tightness, be 0.07～0.08Mpa, temperature is under 120～130 ℃, to stir 2～3 hours, then add aliphatic isocyanates, temperature is down to 80 degrees centigrade, insulation reaction 2.5 hours, and then input organotin catalysts, continue reaction after 1 hour, be cooled to 60 degrees centigrade, then discharging sealing are preserved and are got final product, wherein:
Polyether glycol accounts for polyether glycol, castor oil polyhydric alcohol, liquid copolymeric polyester polyvalent alcohol, four kinds of 10-80% that drop into the material total amount of aliphatic isocyanates;
Castor oil polyhydric alcohol accounts for polyether glycol, castor oil polyhydric alcohol, liquid copolymeric polyester polyvalent alcohol, four kinds of 5-25% that drop into the material total amount of aliphatic isocyanates;
Aliphatic isocyanates accounts for polyether glycol, castor oil polyhydric alcohol, liquid copolymeric polyester polyvalent alcohol, four kinds of 5-40% that drop into the material total amount of aliphatic isocyanates;
All the other are liquid copolymerization polyester polyvalent alcohol, and liquid copolymerization polyester polyvalent alcohol accounts for polyether glycol, castor oil polyhydric alcohol, liquid copolymeric polyester polyvalent alcohol, four kinds of ratios that drop into the material total amount of aliphatic isocyanates more than or equal to 5%;
The organotin catalysts ratio is more than or equal to 0.1%.
Described polyether glycol is the multipolymer of polyoxyethylene glycol and polytetrahydrofuran, and polyether glycol accounts for polyether glycol, castor oil polyhydric alcohol, liquid copolymeric polyester polyvalent alcohol, four kinds of 20-70% that drop into the material total amount of aliphatic isocyanates.
The molecular weight of described castor oil polyhydric alcohol is 700, and castor oil polyhydric alcohol accounts for polyether glycol, castor oil polyhydric alcohol, liquid copolymeric polyester polyvalent alcohol, four kinds of 5-15% that drop into the material total amount of aliphatic isocyanates.
Described aliphatic isocyanates is l, one or both in hexamethylene-diisocyanate, isophorone diisocyanate, aliphatic isocyanates account for polyether glycol, castor oil polyhydric alcohol, liquid copolymeric polyester polyvalent alcohol, four kinds of 12-20% that drop into the material total amount of aliphatic isocyanates.
Described liquid copolymerization polyester polyvalent alcohol is obtained by method production once: in the reactor with vacuum dewatering plant, thermometer, agitator and condensing works, add hexanodioic acid, 2,4-diethyl-1, the 5-pentanediol, the 2-methyl isophthalic acid, the 8-ethohexadiol, wherein the mol ratio of two kinds of glycol can be 0.2～1.8; The mol ratio of glycol and hexanodioic acid can be 1.18～1.05; Catalyzer uses dibutyl tin laurate, and add-on is 0.08～0.1% of reaction-ure mixture, heats up and starts simultaneously to stir; When being warmed up to 190 ℃, start to distillate moisture, continue to be warming up to interior temperature and reach 220 ℃, while measuring acid number less than 15mg/KOH, start to reduce pressure to steam and react oligopolymer and the unnecessary alcohol that generates, when overhead product reduced or be slack-off, the high vacuum reaction was carried out in decompression, and system pressure remains on below 80Pa, in 3 hours reaction times, polycondensation finishes.Under nitrogen protection, remove the vacuum discharging and obtain liquid copolyester polyvalent alcohol.
The production method of the resulting curable transparent yellowing-resistant base polyurethane prepolymer for use as of the present invention, use polyether glycol, castor oil polyhydric alcohol and three kinds of polyol groups of liquid copolymeric polyester polyol and, and use aliphatic isocyanates synthesis of polyurethane prepolymer, this performed polymer is fully transparent after solidifying, owing to having avoided using polyisocyanates composition such as toluene two isocyanides that contain the phenyl ring composition, after gluing, glue-line is difficult for xanthochromia through illumination simultaneously.Used simultaneously the polyfunctionality compositions such as castor oil derivative, the performed polymer mechanical property is enhanced.This performed polymer does not contain solvent, nontoxic, tasteless; Use this performed polymer configuration moisture-curable polyurethane tackiness agent, best gluing temperature is at 70～90 ℃, various physical behaviors are identical with the coating process of polyolefin hot-melt, but therefore gluing temperature decrease produces initial strength faster than polyolefin hot-melt glue; After gluing, rely on colloid inside to exist in active isocyanate group and environment and adherend surface minute moisture reaction generation curing cross-linked, significantly improve the final bonding strength of glue.
Embodiment
The present invention is further described by the following embodiment.
Embodiment 1:
The production method of the curable transparent yellowing-resistant base polyurethane prepolymer for use as that the present embodiment is described, at first in the reactor that thermometer, agitator and condensing works are housed with vacuum dewatering plant, add hexanodioic acid 146.1g, 2,4-diethyl-1,5-pentanediol 80g, 2-methyl isophthalic acid, 8-ethohexadiol 90g, catalyzer dibutyl tin laurate 0.3g, heat up and start simultaneously to stir; When being warmed up to 190 ℃ of left and right, start to distillate moisture, continue to be warming up to interior temperature and reach 220 ℃, water to be distillated near theoretical amount the time, while measuring acid number less than 15mg/KOH, starting to reduce pressure steams oligopolymer and the unnecessary alcohol that reaction generates, when overhead product reduces or become unrestrained, the high vacuum reaction is carried out in decompression, system pressure remains on below 80Pa, and in 3 hours reaction times, polycondensation finishes.Under nitrogen protection, remove the vacuum discharging and obtain liquid copolyester polyvalent alcohol 1; With same method: in the reactor that thermometer, agitator and condensing works be housed of 500mL with vacuum dewatering plant, adding hexanodioic acid 146.1g, 2,4-diethyl-1,5-pentanediol 70g, the 2-methyl isophthalic acid, 8-ethohexadiol 100g, catalyzer dibutyl tin laurate 0.3g, heat up and start simultaneously to stir; When being warmed up to 190 ℃ of left and right, start to distillate moisture, continue to be warming up to interior temperature and reach 220 ℃, water to be distillated near theoretical amount the time, while measuring acid number less than 15mg/KOH, starting to reduce pressure steams oligopolymer and the unnecessary alcohol that reaction generates, when overhead product reduces or become unrestrained, the high vacuum reaction is carried out in decompression, system pressure remains on below 80Pa, and in 3 hours reaction times, polycondensation finishes.Under nitrogen protection, remove the vacuum discharging and obtain liquid copolyester polyvalent alcohol 2; And then to 500mL with in the reactor of vacuum dewatering plant, thermometer, agitator and condensing works, dropping into the 200g polyether glycol, the 35g castor oil polyhydric alcohol, 50g copolyester polyvalent alcohol 1,50g copolyester polyvalent alcohol 2 is that 0.07～0.08Mpa, temperature are to stir and dewatered 3 hours under 120～130 ℃ in vacuum tightness; Then the isophorone diisocyanate that adds 75g, 80 ℃, insulation reaction 2.5 hours; Then drop into 0.5g catalyzer dibutyl tin laurate and continue reaction after 1 hour, titration NCO, be cooled to 60 ℃, and discharging sealing are preserved and got final product.
Embodiment 2:
The production method of the curable transparent yellowing-resistant base polyurethane prepolymer for use as that the present embodiment is described, in the reactor with vacuum dewatering plant, thermometer, agitator and condensing works, drop into the 200g polyether glycol, the 45g castor oil polyhydric alcohol, 10g copolyester polyvalent alcohol 1,40g copolyester polyvalent alcohol 2 is that 0.07～0.08Mpa, temperature are to stir and dewatered 3 hours under 120～130 ℃ in vacuum tightness; Then the isophorone diisocyanate that adds 75g, 80 ℃, insulation reaction 2.5 hours; Then drop into 0.3g catalyzer dibutyl tin laurate and continue reaction after 1 hour, the titration nco value reaches design load, is cooled to 60 ℃, and discharging sealing are preserved and got final product.
Embodiment 3:
The production method of the curable transparent yellowing-resistant base polyurethane prepolymer for use as that the present embodiment is described, in reactor, drop into the 100g polyether glycol, the 5g castor oil polyhydric alcohol, 200g copolyester polyvalent alcohol 1 is that 0.07～0.08Mpa, temperature are to stir and dewatered 3 hours under 120～130 ℃ in vacuum tightness; Then add the 65g isophorone diisocyanate, 80 ℃ of insulation reaction 2.5 hours; Then drop into 0.3g catalyzer dibutyl tin laurate and continue reaction after 1 hour, the titration nco value reaches design load, is cooled to 60 ℃, and discharging sealing are preserved and got final product.
Embodiment 4:
The production method of the curable transparent yellowing-resistant base polyurethane prepolymer for use as that the present embodiment is described, in reactor, drop into the 200g polyether glycol, the 35g castor oil polyhydric alcohol, the liquid copolyester polyvalent alcohol 2 of 100g is that 0.07～0.08Mpa, temperature are to stir and dewatered 3 hours under 120～130 ℃ in vacuum tightness; Then the isophorone diisocyanate that adds 62g, temperature are down to 80 ℃, insulation reaction 2.5 hours; Then drop into 0.3g catalyzer dibutyl tin laurate and continue reaction after 1 hour, titration NCO, be cooled to 60 ℃, and discharging sealing are preserved and got final product.
Comparative Examples 1:
In reactor, drop into the commercially available poly-hexanodioic acid hexylene glycol ester of 100g, the poly-hexanodioic acid 1,2-PD ester that 55g is commercially available, the polyethylene glycol adipate that 96g is commercially available).In vacuum tightness, be that 0.07～0.08Mpa, temperature are to stir and dewatered 3 hours under 120～130 ℃; Then add 4 of 65g, and the 4-MDI (4,4-MDI), 70 ℃ of insulation reaction 2.5 hours; Then drop into 0.3g catalyzer dibutyl tin laurate continuation reaction and be cooled to 90 ℃ after 1 hour, discharging sealing are preserved.
Comparative Examples 2:
To dropping into the commercially available polyethylene glycol adipate of 100g in reactor, the polydiethylene glycol adipate that 55g is commercially available, the commercially available poly-hexanodioic acid of 96g-2-methyl isophthalic acid, ammediol ester).In vacuum tightness, be that 0.07～0.08Mpa, temperature are to stir and dewatered 3 hours under 120～130 ℃; Then add 4 of 65g, and the 4-MDI (4,4-MDI), 70 ℃ of insulation reaction 2.5 hours; Then drop into 0.3g catalyzer dibutyl tin laurate continuation reaction and be cooled to 90 ℃ after 1 hour, discharging sealing are preserved.
Table 1: performed polymer character
The bonding PVC sheet of 1:PVC
2: 0.5cm thickness masking after use solidifying, translucent or the 3=that turns white is fully transparent according to the complete opaque 2=of following standard evaluation: 1=
3: use and solidify rear 0.2cm thickness masking, be placed in outdoor visible light place 90 days, according to the translucent 3=of the yellow micro-Huang of opaque 2=of following standard evaluation: 1=transparent not yellowing fully
As can be seen from Table 1, the transparency that the performed polymer that is made by the method for the invention has had and anti-yellowing property, mechanical property close to by aromatic isocyanate (as 4,4-MDI), performed polymer molten state viscosity is lower simultaneously, and moisture-curable speed is relatively low, is convenient to use under low temperature.
Claims (6)
1. the production method of a curable transparent yellowing-resistant base polyurethane prepolymer for use as, it is characterized in that: in reactor, drop into polyether glycol, castor oil polyhydric alcohol and liquid copolymeric polyester polyvalent alcohol, in vacuum tightness, be that 0.07～0.08Mpa, temperature are under 120～130 ℃, to stir 2～3 hours, then add aliphatic isocyanates, temperature is down to 80 ℃, insulation reaction 2.5 hours, and then input organotin catalysts, continue reaction after 1 hour, be cooled to 60 ℃, then discharging sealing are preserved and are got final product; Wherein:
Polyether glycol accounts for polyether glycol, castor oil polyhydric alcohol, liquid copolymeric polyester polyvalent alcohol, four kinds of 10-80% that drop into the material total amount of aliphatic isocyanates;
Castor oil polyhydric alcohol accounts for polyether glycol, castor oil polyhydric alcohol, liquid copolymeric polyester polyvalent alcohol, four kinds of 5-25% that drop into the material total amount of aliphatic isocyanates;
Aliphatic isocyanates accounts for polyether glycol, castor oil polyhydric alcohol, liquid copolymeric polyester polyvalent alcohol, four kinds of 5-40% that drop into the material total amount of aliphatic isocyanates;
All the other are liquid copolymerization polyester polyvalent alcohol, and liquid copolymerization polyester polyvalent alcohol accounts for polyether glycol, castor oil polyhydric alcohol, liquid copolymeric polyester polyvalent alcohol, four kinds of ratios that drop into the material total amount of aliphatic isocyanates more than or equal to 5%;
The organotin catalysts ratio is more than or equal to 0.1%.
2. the production method of a kind of curable transparent yellowing-resistant base polyurethane prepolymer for use as according to claim 1, it is characterized in that: described polyether glycol is the multipolymer of polyoxyethylene glycol and polytetrahydrofuran, and polyether glycol accounts for polyether glycol, castor oil polyhydric alcohol, liquid copolymeric polyester polyvalent alcohol, four kinds of 20-70% that drop into the material total amount of aliphatic isocyanates.
3. the production method of 2 arbitrary described a kind of curable transparent yellowing-resistant base polyurethane prepolymer for use as according to claim 1,, it is characterized in that: the molecular weight of described castor oil polyhydric alcohol is 700, and castor oil polyhydric alcohol accounts for polyether glycol, castor oil polyhydric alcohol, liquid copolymeric polyester polyvalent alcohol, four kinds of 5-15% that drop into the material total amount of aliphatic isocyanates.
4. the production method of 2 arbitrary described a kind of curable transparent yellowing-resistant base polyurethane prepolymer for use as according to claim 1,, it is characterized in that: described liquid copolymerization polyester polyvalent alcohol is obtained by method production once: in the reactor with vacuum dewatering plant, thermometer, agitator and condensing works, add hexanodioic acid, 2,4-diethyl-1, the 5-pentanediol, the 2-methyl isophthalic acid, the 8-ethohexadiol, wherein the mol ratio of two kinds of glycol can be 0.2～1.8; The mol ratio of glycol and hexanodioic acid can be 1.18～1.05; Catalyzer uses dibutyl tin laurate, and add-on is 0.08～0.1% of reaction-ure mixture, heats up and starts simultaneously to stir; When being warmed up to 190 ℃, start to distillate moisture, continue to be warming up to interior temperature and reach 220 ℃, while measuring acid number less than 15mg/KOH, start to reduce pressure to steam and react oligopolymer and the unnecessary alcohol that generates, when overhead product reduced or be slack-off, the high vacuum reaction was carried out in decompression, and system pressure remains on below 80Pa, in 3 hours reaction times, polycondensation finishes.Under nitrogen protection, remove the vacuum discharging and obtain liquid copolyester polyvalent alcohol.
5. the production method of a kind of curable transparent yellowing-resistant base polyurethane prepolymer for use as according to claim 3, it is characterized in that: described liquid copolymerization polyester polyvalent alcohol is obtained by method production once: in the reactor with vacuum dewatering plant, thermometer, agitator and condensing works, add hexanodioic acid, 2,4-diethyl-1, the 5-pentanediol, the 2-methyl isophthalic acid, the 8-ethohexadiol, wherein the mol ratio of two kinds of glycol can be 0.2～1.8; The mol ratio of glycol and hexanodioic acid can be 1.18～1.05; Catalyzer uses dibutyl tin laurate, and add-on is 0.08～0.1% of reaction-ure mixture, heats up and starts simultaneously to stir; When being warmed up to 190 ℃, start to distillate moisture, continue to be warming up to interior temperature and reach 220 ℃, while measuring acid number less than 15mg/KOH, start to reduce pressure to steam and react oligopolymer and the unnecessary alcohol that generates, when overhead product reduced or be slack-off, the high vacuum reaction was carried out in decompression, and system pressure remains on below 80Pa, in 3 hours reaction times, polycondensation finishes.Under nitrogen protection, remove the vacuum discharging and obtain liquid copolyester polyvalent alcohol.
6. the production method of 2 arbitrary described a kind of curable transparent yellowing-resistant base polyurethane prepolymer for use as according to claim 1,, it is characterized in that: described aliphatic isocyanates is l, one or both in hexamethylene-diisocyanate, isophorone diisocyanate, aliphatic isocyanates account for polyether glycol, castor oil polyhydric alcohol, liquid copolymeric polyester polyvalent alcohol, four kinds of 12-20% that drop into the material total amount of aliphatic isocyanates.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310278379.8A CN103396526B (en) | 2013-07-03 | 2013-07-03 | The production method of curable transparent yellowing-resistant base polyurethane prepolymer for use as |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310278379.8A CN103396526B (en) | 2013-07-03 | 2013-07-03 | The production method of curable transparent yellowing-resistant base polyurethane prepolymer for use as |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103396526A true CN103396526A (en) | 2013-11-20 |
| CN103396526B CN103396526B (en) | 2015-12-09 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105002738A (en) * | 2015-06-30 | 2015-10-28 | 陕西科技大学 | Preparation method and application method of solvent-free moisture-curable resin for synthetic leather |
| CN106675495A (en) * | 2016-12-01 | 2017-05-17 | 苏州金枪新材料股份有限公司 | Crylic acid yellow-resistant Polyurethane (PUR) adhesive and preparation method |
| CN109776028A (en) * | 2019-03-11 | 2019-05-21 | 东莞市浩展高分子材料有限公司 | A kind of gluing stone porous pavement material and its construction method |
| CN113105804A (en) * | 2021-03-05 | 2021-07-13 | 广东美涂士建材股份有限公司 | Fluorescent colorful paint |
| CN113105794A (en) * | 2021-03-05 | 2021-07-13 | 广东美涂士建材股份有限公司 | Porous art coating |
| CN113105797A (en) * | 2021-03-05 | 2021-07-13 | 广东美涂士建材股份有限公司 | Paint for art decoration |
| CN115124966A (en) * | 2021-03-24 | 2022-09-30 | 民权县星健体育器材有限公司 | Polyurethane glue and preparation process thereof |
| US11806892B2 (en) | 2017-06-14 | 2023-11-07 | Wanhua Chemical Group Co., Ltd. | No-added formaldehyde binder for composite wood product and the composite wood product manufactured by the same |
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| CN102924683A (en) * | 2012-11-22 | 2013-02-13 | 山西省应用化学研究所 | Aqueous polyurethane dispersoid for coating yellowing-resistant leather and preparation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105002738A (en) * | 2015-06-30 | 2015-10-28 | 陕西科技大学 | Preparation method and application method of solvent-free moisture-curable resin for synthetic leather |
| CN106675495A (en) * | 2016-12-01 | 2017-05-17 | 苏州金枪新材料股份有限公司 | Crylic acid yellow-resistant Polyurethane (PUR) adhesive and preparation method |
| US11806892B2 (en) | 2017-06-14 | 2023-11-07 | Wanhua Chemical Group Co., Ltd. | No-added formaldehyde binder for composite wood product and the composite wood product manufactured by the same |
| CN109776028A (en) * | 2019-03-11 | 2019-05-21 | 东莞市浩展高分子材料有限公司 | A kind of gluing stone porous pavement material and its construction method |
| CN113105804A (en) * | 2021-03-05 | 2021-07-13 | 广东美涂士建材股份有限公司 | Fluorescent colorful paint |
| CN113105794A (en) * | 2021-03-05 | 2021-07-13 | 广东美涂士建材股份有限公司 | Porous art coating |
| CN113105797A (en) * | 2021-03-05 | 2021-07-13 | 广东美涂士建材股份有限公司 | Paint for art decoration |
| CN115124966A (en) * | 2021-03-24 | 2022-09-30 | 民权县星健体育器材有限公司 | Polyurethane glue and preparation process thereof |
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| Publication number | Publication date |
|---|---|
| CN103396526B (en) | 2015-12-09 |
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Address after: 314500, No. 299, entrepreneurial road, Shimen Town, Jiaxing City, Zhejiang, Tongxiang Patentee after: Zhejiang Jian like Polymer Technology Co.,Ltd. Address before: 314500, No. 299, entrepreneurial road, Shimen Town, Jiaxing City, Zhejiang, Tongxiang Patentee before: ZHEJIANG JOYA CHEMICAL Co.,Ltd. |
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Correction item: Patentee|Address Correct: ZHEJIANG JOYA POLYMER TECHNOLOGY CO., LTD.|314500, No. 299, entrepreneurial road, Shimen Town, Jiaxing City, Zhejiang, Tongxiang False: Zhejiang Jian like Polymer Technology Co Ltd|314500, No. 299, entrepreneurial road, Shimen Town, Jiaxing City, Zhejiang, Tongxiang Number: 15 Volume: 32 |