CN102432811A

CN102432811A - High-stability diphenyl-methane-diisocyanate (MDI)-trimethylolpropane (TMP) polyurethane

Info

Publication number: CN102432811A
Application number: CN2011102496686A
Authority: CN
Inventors: 钱华; 张林荣
Original assignee: WUJIANG BEISHE SHENGYUAN TEXTILE AUXILIARIES FACTORY
Current assignee: WUJIANG BEISHE SHENGYUAN TEXTILE AUXILIARIES FACTORY
Priority date: 2011-08-29
Filing date: 2011-08-29
Publication date: 2012-05-02

Abstract

The invention discloses high-stability diphenyl-methane-diisocyanate (MDI)-trimethylolpropane (TMP) polyurethane. The high-stability MDI-TMP polyurethane is obtained by the following steps of: heating TMP and acetic ether to reflux respectively, and dehydrating for 1 to 2 hours to obtain dehydrated TMP and dehydrated acetic ether respectively; adding dehydrated acetic ether into an agitated reactor filled with nitrogen or carbon dioxide, adding 4,4-MDI and 2,4-MDI in a weight ratio of (2-5):1, heating to the temperature to 40 to 50 DEG C, stirring and dissolving completely, and adding a small amount of sodium methoxide and lithium oxide; and slowly adding the dehydrated TMP by different steps in 1 to 2 hours, reacting at the temperature of 70 DEG C for 3 to 4 hours, and adding a trace amount of phosphoric acid to obtain a prepolymer product; and adding sodium hydrogensulfite and reacting for 1 to 2 hours, adding a small amount of 2,6-di-tert-butyl-4-methylphenol, and finally adjusting pH value to 4.5. The MDI-TMP polyurethane is more environment-friendly, does not influence a human body and is high in stability.

Description

High stability MDI-TMP type polyurethane

Technical field

The invention belongs to field of textiles, relate in particular to the application of whole stain in the weaving.

Background technology

Urethane is because therefore its paint film good mechanical property, tough and tensile, wear-resisting, plentiful, bright can have purposes widely, especially in synthon and textile finshing agent field in low-temperature curing.But traditional urethane all is to adopt TDI (tolylene diisocyanate) to be raw material; Because TDI is toxic; Thereby in textile printing and dyeing, unavoidably can residually there be the free TDI monomer that human body is exerted an influence, simultaneously in the urethane-the NCO group very vivaciously can react with hydrogen bond, simultaneously-NCO group self also assembles dimer synthon; Therefore the urethane that generates is generally stable inadequately, is difficult to prolonged preservation.

Summary of the invention

Goal of the invention: the defective to above-mentioned existence, the invention provides a kind of employing MDI (diphenylmethanediisocyanate) and analogue thereof as raw material, prepared a kind of high stability MDI-TMP type polyurethane.

Technical scheme: for realizing the foregoing invention purpose; The present invention adopts following technical scheme: a kind of high stability MDI-TM P type polyurethane; It makes through following steps: a, processed: TMP and vinyl acetic monomer are carried out reflux respectively, the 1 ~ 2h that dewaters obtain respectively dewatering TMP and dehydration acetate ethyl ester;

B, in the reaction kettle that is full of nitrogen or carbonic acid gas, add earlier the dehydration acetate ethyl ester; Add weight ratio then and be 2 ~ 5:1 4,4-diphenylmethanediisocyanate and 2,4-diphenylmethanediisocyanate; Be heated to 40 ~ 50 ℃; After stirring dissolving fully, add a spot of sodium methylate and Lithium Oxide 98min; C, substep slowly adds dehydration TMP in 1 ~ 2 hour then, and at 70 ℃ down behind reaction 3 ~ 4h, the phosphoric acid that adds trace obtains prepolymer product; D, in step b, obtain to add in the prepolymer product sodium sulfite anhy 96 reaction 1 ~ 2h after, add a spot of 2,6-di-tert-butyl-4-methy phenol, regulating the pH value at last is 4.5, promptly gets high stability MDI-TMP type polyurethane.

Beneficial effect: compared with prior art, the present invention has the following advantages: owing to adopt hypotoxicity material such as MDI as raw material, therefore environmental protection more can not exert an influence to human body; Simultaneously 2, the 4-diphenylmethanediisocyanate has asymmetrical-NCO group, can reduce base polyurethane prepolymer for use as from the crystallization possibility, thereby improved the stability of product greatly.

Embodiment

Below in conjunction with embodiment, technical scheme of the present invention is elaborated, but protection scope of the present invention is not limited to said embodiment.

In having the container of reflux, drop into TMP and vinyl acetic monomer respectively, the reflux 1h that dewaters under the condition of vacuumizing, TMP and dehydration acetate ethyl ester obtain dewatering; After in being full of the reaction kettle of nitrogen, adding the dehydration acetate ethyl ester in addition; When stirring, add weight ratio and be 5:1 4,4-diphenylmethanediisocyanate and 2,4-diphenylmethanediisocyanate; Be heated to 40 ~ 50 ℃; After stirring dissolving fully, add the sodium methylate of trace and the Lithium Oxide 98min of catalytic amount; Substep slowly adds dehydration TMP (this process control is in little 2 hours) then, and behind elevated temperature to 70 ℃ reaction 3 ~ 4h, the phosphoric acid that adds trace obtains prepolymer product; After then adding weight ratio and be sodium sulfite anhy 96 reaction 1 ~ 2h of 0.08%, add a spot of 2,6-di-tert-butyl-4-methy phenol, using the phosphorus acid for adjusting pH value at last is 4.5, promptly gets high stability MDI-TMP type polyurethane.。

The high stability MDI-TMP type polyurethane that aforesaid method obtains is a light yellow transparent liquid, and sealing was preserved after 12 months, be yellow transparent liquid still, and does not see that change is arranged is muddy.

Claims

1. high stability MDI-TMP type polyurethane is characterized in that making through following steps:

A, processed: TMP and vinyl acetic monomer are carried out reflux respectively, the 1 ~ 2h that dewaters obtain respectively dewatering TMP and dehydration acetate ethyl ester;

B, in the reaction kettle that is full of nitrogen or carbonic acid gas, add earlier the dehydration acetate ethyl ester; Add weight ratio then and be 2 ~ 5:1 4,4-diphenylmethanediisocyanate and 2,4-diphenylmethanediisocyanate; Be heated to 40 ~ 50 ℃; After stirring dissolving fully, add a spot of sodium methylate and Lithium Oxide 98min;

C, substep slowly adds dehydration TMP in 1 ~ 2 hour then, and at 70 ℃ down behind reaction 3 ~ 4h, the phosphoric acid that adds trace obtains prepolymer product;

D, in step b, obtain to add in the prepolymer product sodium sulfite anhy 96 reaction 1 ~ 2h after, add a spot of 2,6-di-tert-butyl-4-methy phenol, regulating the pH value at last is 4.5, promptly gets high stability MDI-TMP type polyurethane.

2. according to the said high stability MDI-TMP type polyurethane of claim 1, it is characterized in that: the gross weight of said 4,4-diphenylmethanediisocyanate and 2,4-diphenylmethanediisocyanate is 2 ~ 3:1 with the weight ratio of dehydration TMP.