CN101402717A

CN101402717A - Enclosed polyurethane performed polymer for formulating low-temperature plasticizing PVC plastic colloidal sols and method of producing the same

Info

Publication number: CN101402717A
Application number: CNA2008101945277A
Authority: CN
Inventors: 匡建钢
Original assignee: Individual
Current assignee: Individual
Priority date: 2008-10-30
Filing date: 2008-10-30
Publication date: 2009-04-08

Abstract

The invention relates to a close type polyurethane prepolymer used for preparing low temperature plasticizing PVC plastisol, which can improve the adhesion of the PVC plastisol on an electrophoresis paint plate and simultaneously reduce the plasticizing temperature of the PVC plastisol so as to reduce energy consumption. The polyurethane prepolymer is characterized in that: the polyurethane prepolymer is polymerized by polyisocyanate and a polyhydroxy compound with the generation terminal group of the semi-prepolymer of - NCO and a sealant is applied to blocking the semi-prepolymer so as to obtain the close type polyurethane prepolymer. The preparation method is as follows: 50 portions to 500 portions of a diluent are added into a three-necked reactor, stirred and heated to 75 DEG C to 80 DEG C, then 100 portions to 400 portions of polyisocyanate are added, 250 portions to 800 portions of the polyhydroxy compound are added slowly, reaction lasts for 3 hours to 4 hours, then 10 portions to 200 portions of the sealant and 0 portion to 2 portions of a catalyst are added slowly and the reaction lasts for 2 hours and 3 hours.

Description

Enclosed polyurethane performed polymer of formulating low-temperature plasticizing PVC plastic colloidal sols and preparation method thereof

Technical field

The present invention relates to base polyurethane prepolymer for use as and preparation method thereof field, be specially enclosed polyurethane performed polymer of formulating low-temperature plasticizing PVC plastic colloidal sols and preparation method thereof.

Background technology

Pvc plastisol is widely used in automobile industry, its typical products is that the anti-stone of PVC hits car base paint and PVC weld seam seal gum, the required plasticization temperature of pvc plastisol product in the market is mostly about 140 ℃, the expensive goods plasticization temperature can be low to moderate about 130 ℃, auto producer need reduce the drying room temperature for the purpose of energy-saving and emission-reduction, not only can improve the sticking power of pvc plastisol on the electrocoating paint plate, simultaneously but also can reduce the low-temperature plasticizing PVC plastic colloidal sols of the plasticization temperature of pvc plastisol so need to use; Enclosed polyurethane performed polymer is a kind of urethane resin, urethane resin is a kind of macromolecular compound with special performance and many-sided purposes, contain in its molecular chain the high isocyanate group of polarity (NCO) and carbamate (NHCOO-), with the material that contains active hydrogen good adhesive capacity is arranged, and and produced hydrogen bond action between the sticking material, intramolecular force is strengthened, make bonding more firm, so tackifier of Chang Zuowei pvc plastisol, with the sticking power of raising pvc plastisol on the electrocoating paint plate, but it does not reach the effect that reduces the PVC plasticization temperature; Performed polymer on the market is a main raw with isocyanate-monomer or its affixture generally, direct and encapsulant prepared in reaction performed polymer, and it is mainly as the solidifying agent that paints.

Summary of the invention

At the problems referred to above, the invention provides the enclosed polyurethane performed polymer of formulating low-temperature plasticizing PVC plastic colloidal sols, it can improve the sticking power of pvc plastisol on the electrocoating paint plate, reduce the plasticization temperature of pvc plastisol simultaneously, make pvc plastisol under the baking condition about 120 ℃, ideal sticking power and mechanical property can be reached, and xanthochromia can not be produced.If automobile factory uses the pvc plastisol of this low-temperature plasticizing type instead, then its drying room temperature can be reduced about 20 ℃, can reach the purpose of energy-saving and emission-reduction, the present invention also provides the preparation method of the enclosed polyurethane performed polymer of formulating low-temperature plasticizing PVC plastic colloidal sols for this reason.

The enclosed polyurethane performed polymer of formulating low-temperature plasticizing PVC plastic colloidal sols is characterized in that: it is by polyisocyanates and polyol polymerization, generates end group to be-semi-prepolymer of NCO, and reaction formula is: 2OCN-R ₁-NCO+HO-R ₂-OH → R ₂(OOC-NH-R ₁-NCO) ₂, and then with encapsulant described semi-prepolymer is carried out end-blocking and obtain enclosed polyurethane performed polymer, reaction formula is:

R ₂(OOC-NH-R ₁-NCO) ₂+2BH→R ₂(OOC-NH-R ₁-NH-CO-B) ₂。

It is further characterized in that: in the above-mentioned polyreaction, described polyisocyanic acid ester content is 100 parts～400 parts, and described polyol content is 250 parts～800 parts, and described encapsulant content is 10 parts～200 parts;

It further is characterised in that: preferred isophorone diisocyanate of described polyisocyanates (IPDI) and derivative thereof, also can select tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), 2,6-vulcabond methylhexanoic acid ester (LDI), xylylene diisocyanate (XDI), naphthalene-1,5-vulcabond (NDI), 1,6-hexamethylene-diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexyl methane diisocyanate (H ₁₂MDI), tetramethylxylylene diisocyanate (TMXDI) etc.; Described polyol preferred, polyethers polyvalent alcohol also can be selected polyester polyol, Resins, epoxy, polyurea polylol, polytetrahydrofuran and copolyether polyvalent alcohol thereof, polyacrylate polyol, polyolefin polyhydric alcohol, vegetable oil polyol etc.; The preferred dimethyl pyrazole of described encapsulant also can be selected for use and can select ethanol, phenol, hexanolactam, diethyl malonate, acetoxime, methyl ethyl ketone oxime, sodium bisulfite, pyrazoles, triazole, methyl ethyl diketone, imidazoles, amine etc.

The preparation method of the enclosed polyurethane performed polymer of formulating low-temperature plasticizing PVC plastic colloidal sols: the thinner that at first in three neck reactors, adds 50 parts～500 parts, warming while stirring to 75 ℃～80 ℃, the polyisocyanates that adds 100 parts～400 parts then, the polyol reaction that slowly adds 250 parts～800 parts again is after 3 hours～4 hours, and encapsulant and 0 part～2 parts catalyzer of slowly adding 10 parts～200 parts continue reaction 2 hours～3 hours.

Use enclosed polyurethane performed polymer formulating low-temperature plasticizing PVC plastic colloidal sols of the present invention, can effectively reduce the plasticization temperature of pvc plastisol, make pvc plastisol under the baking condition about 120 ℃, can reach ideal sticking power and mechanical property, the use of low-temperature plasticizing PVC plastic colloidal sols, can reduce the drying room temperature, play the effect of energy-saving and emission-reduction.

Embodiment

The enclosed polyurethane performed polymer of formulating low-temperature plasticizing PVC plastic colloidal sols, its composition comprises polyisocyanates, polyol, and it is earlier by polyisocyanates and polyol polymerization, generates end group to be-semi-prepolymer of NCO, and reaction formula is:

2OCN-R ₁-NCO+HO-R ₂-OH→R ₂(OOC-NH-R ₁-NCO) ₂，

And then with encapsulant described semi-prepolymer is carried out end-blocking and obtain enclosed polyurethane performed polymer, reaction formula is: R ₂(OOC-NH-R ₁-NCO) ₂+ 2BH → R ₂(OOC-NH-R ₁-NH-CO-B) ₂,

Wherein the polyisocyanic acid ester content is 100 parts～400 parts, and optimum content is 250 parts; Polyol content is 250 parts～800 parts, and optimum content is 525 parts; Encapsulant content is 10 parts～200 parts, and optimum content is 105 parts; Preferred isophorone diisocyanate of polyisocyanates (IPDI) and derivative thereof, its toxicity is little than the polyisocyanates of other type, also can select tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), 2,6-vulcabond methylhexanoic acid ester (LDI), xylylene diisocyanate (XDI), naphthalene-1,5-vulcabond (NDI), 1,6-hexamethylene-diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexyl methane diisocyanate (H ₁₂MDI), tetramethylxylylene diisocyanate (TMXDI) etc.; Polyol preferred, polyethers polyvalent alcohol, its product is better flexible, also can select polyester polyol, Resins, epoxy, polyurea polylol, polytetrahydrofuran and copolyether polyvalent alcohol thereof, polyacrylate polyol, polyolefin polyhydric alcohol, vegetable oil polyol etc.; The preferred dimethyl pyrazole of described encapsulant, its enclosed height and deblocking temperature are low, also can select for use and can select ethanol, phenol, hexanolactam, diethyl malonate, acetoxime, methyl ethyl ketone oxime, sodium bisulfite, pyrazoles, triazole, methyl ethyl diketone, imidazoles, amine etc.;

The deblocking reaction formula of enclosed polyurethane performed polymer is:

R2(OOC-NH-R1-NH-CO-B)2→R2(OOC-NH-R1-NCO)2+2BH。

Below in conjunction with specific embodiment the course of processing of the present invention is described:

Embodiment one:

The thinner that at first in three neck reactors, adds 50 parts, warming while stirring to 75 ℃ adds 100 parts isophorone diisocyanate then, the polyether glycol reaction that slowly adds 250 parts more slowly added 10 parts of dimethyl pyrazoles and continues reaction 2 hours after 3 hours.

Embodiment two:

The thinner that at first in three neck reactors, adds 300 parts, warming while stirring to 77 ℃ adds 250 parts isophorone diisocyanate then, the polyether glycol reaction that slowly adds 500 parts again is after 3.5 hours, slowly adds dimethyl pyrazole and 1 part of catalyzer of 110 and continues reaction 2.5 hours.

Embodiment three:

The thinner that at first in three neck reactors, adds 500 parts, warming while stirring to 80 ℃ adds 400 parts isophorone diisocyanate then, the polyether glycol reaction that slowly adds 800 parts again is after 4 hours, slowly adds dimethyl pyrazole and 2 parts of catalyzer of 200 and continues reaction 3 hours.

In the foregoing description, thinner is selected 2-Butoxyethyl acetate for use, and it is nontoxic and solvability good, also can select dimethylbenzene, N-BUTYL ACETATE, ethylene glycol ether acetate, pimelinketone, dioctyl phthalate (DOP), diisononyl phthalate etc. for use; Catalyzer is selected organism compound dibutyl tin laurate for use, and its cost is lower, and excellent catalytic effect, also can select tertiary amine compounds for use, as triethylenediamine, cyclohexyl methyl tertiary amine, tetramethyl-Alkylenediamine, dimethylethanolamine etc.

Claims

1, the enclosed polyurethane performed polymer of formulating low-temperature plasticizing PVC plastic colloidal sols is characterized in that: it is by polyisocyanates and polyol polymerization, generates end group to be-semi-prepolymer of NCO, and reaction formula is: 2OCN-R ₁-NCO+HO-R ₂-OH → R ₂(OOC-NH-R ₁-NCO) ₂, and then with encapsulant described semi-prepolymer is carried out end-blocking and obtain enclosed polyurethane performed polymer, reaction formula is:

R ₂(OOC-NH-R ₁-NCO) ₂+2BH→R ₂(OOC-NH-R ₁-NH-CO-B) ₂。

2, the enclosed polyurethane performed polymer of formulating low-temperature plasticizing PVC plastic colloidal sols according to claim 1, it is characterized in that: in the described polyreaction, described polyisocyanic acid ester content is 100 parts～400 parts, described polyol content is 250 parts～800 parts, and described encapsulant content is 10 parts～200 parts.

3, the enclosed polyurethane performed polymer of formulating low-temperature plasticizing PVC plastic colloidal sols according to claim 2, it is characterized in that: preferred isophorone diisocyanate of described polyisocyanates (IPDI) and derivative thereof, also can select tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), 2,6-vulcabond methylhexanoic acid ester (LDI), xylylene diisocyanate (XDI), naphthalene-1,5-vulcabond (NDI), 1,6-hexamethylene-diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexyl methane diisocyanate (H ₁₂MDI), tetramethylxylylene diisocyanate (TMXDI) etc.

4, the enclosed polyurethane performed polymer of formulating low-temperature plasticizing PVC plastic colloidal sols according to claim 3, it is characterized in that: described polyol preferred, polyethers polyvalent alcohol, also can select polyester polyol, Resins, epoxy, polyurea polylol, polytetrahydrofuran and copolyether polyvalent alcohol thereof, polyacrylate polyol, polyolefin polyhydric alcohol, vegetable oil polyol etc.

5, the enclosed polyurethane performed polymer of formulating low-temperature plasticizing PVC plastic colloidal sols according to claim 4, it is characterized in that: the preferred dimethyl pyrazole of described encapsulant, also can select for use and can select ethanol, phenol, hexanolactam, diethyl malonate, acetoxime, methyl ethyl ketone oxime, sodium bisulfite, pyrazoles, triazole, methyl ethyl diketone, imidazoles, amine etc.

6, the preparation method of the enclosed polyurethane performed polymer of formulating low-temperature plasticizing PVC plastic colloidal sols, it is characterized in that: the thinner that in three neck reactors, adds 50 parts～500 parts, warming while stirring to 75 ℃～80 ℃, the polyisocyanates that adds 100 parts～400 parts then, the polyol reaction that slowly adds 250 parts～800 parts again is after 3 hours～4 hours, and encapsulant and 0 part～2 parts catalyzer of slowly adding 10 parts～200 parts continue reaction 2 hours～3 hours.