CN102391460B

CN102391460B - Elastic shape memory polyurethane

Info

Publication number: CN102391460B
Application number: CN 201110249504
Authority: CN
Inventors: 钱华; 张林荣
Original assignee: WUJIANG BEISHE SHENGYUAN TEXTILE AUXILIARIES FACTORY
Current assignee: Shanghai Xin Yuan novel material Science and Technology Ltd.
Priority date: 2011-08-29
Filing date: 2011-08-29
Publication date: 2013-03-20
Anticipated expiration: 2031-08-29
Also published as: CN102391460A

Abstract

The invention discloses elastic shape memory polyurethane, which is prepared through the following steps of: adjusting pH of 50g/L titanium dioxide nanosuspension to be 4.5 by using acetic acid and then ultrasonically dispersing for 30 minutes; adding 10g/L KH550 and heating to 80 DEG C to react for 3 hours; and finally, filtering a reaction product, washing with de-ionized water and then drying,and then crushing into fine grains to obtain modified titanium dioxide catalyst; and b, mixing the obtained modified titanium dioxide catalyst and DMAC (Dimethyl Acetylamide) and then dispersing under the action of ultrasonic wave to obtain catalyst suspension; adding ethyl acetate and MDI (Diphenyl-Methane-Diisocyanate) into a reaction kettle filled with nitrogen gas, heating to 40-50 DEG C, andadding a small amount of sodium methoxide and the catalyst suspension obtained by the step b after full dissolution; then slowly adding TMP (Trimethoprim); reacting at the temperature of 75 DEG C for3-4 hours; and adding a small amount of phosphoric acid. The elastic shape memory polyurethane has high tensile strength and shape recovery rate.

Description

Elastic shape memory 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 its paint film good mechanical property, tough and tensile, wear-resisting, plentiful, bright, can be in low-temperature curing, therefore has widely purposes, and elastic shape memory polyurethane is owing to have high resilience, good shock resistance and adaptability, have again simultaneously wear-resisting, the oil resistant of conventional polyurethanes, anti-ozone, the characteristic such as water-fast, therefore be widely used in biomedical sector, on textile applications, can obtain high waterproof moisture permeating fabric simultaneously.Obtain the catalyzer that these characteristics must be special, usually used nano TiO 2 is owing to have high specific surface area, therefore be a good selection, if but the nano titanic oxide catalyst on the market directly use, then the product performance of acquisition can not be guaranteed.

Summary of the invention

Goal of the invention: for the defective of above-mentioned existence, the invention provides a kind of method of utilizing the modifying titanium dioxide catalyzer to prepare elastic shape memory polyurethane.

Technical scheme: for achieving the above object, the present invention is by the following technical solutions: a kind of elastic shape memory polyurethane, it makes by following steps: the preparation of a, catalyzer: get the nano titanium oxide suspension of 50g/L, and disperse 30min with vinegar acid for adjusting pH to 4.5 is rear with ultrasonic wave; Then add the KH550 of 10g/L, and increase the temperature to 80 ℃ of reaction 3h; At last reaction product is filtered, and use the deionized water wash post-drying, then be ground into fine particle, namely get the modifying titanium dioxide catalyzer; B, with modifying titanium dioxide catalyzer and N that step a obtains, after the N N,N-DIMETHYLACETAMIDE mixes, under hyperacoustic effect, disperse to make the catalyzer suspension; C, in being full of the reactor of nitrogen, add vinyl acetic monomer and MDI, be heated to 40 ~ 50 ℃, after the dissolving, add the catalyzer suspension that a small amount of sodium methylate and step b obtain fully; D, then slowly add TMP, behind 75 ℃ of lower reaction 3 ~ 4h, add a small amount of phosphoric acid.

Specifically, the content of modifying titanium dioxide catalyzer is 10 ~ 50g/L in the described catalyzer suspension of step b.

As to improvement of the technical scheme, more hale the mechanical property of stretching intensity and recovery of shape rate in order to obtain to have, TMP will suitably reduce with respect to the addition of MDI, and therefore the weight ratio of described MDI and TMP is 2 ~ 5:1

Beneficial effect: compared with prior art, the present invention has the following advantages: the urethane that adopts the modifying titanium dioxide catalyzer to obtain has higher tensile strength and recovery of shape rate, therefore belongs to the elastic shape memory polyurethane material.

Embodiment

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

In pure water, slowly pour nano titanium dioxide powder (purchasing the ten thousand scape novel material company limiteds to Hangzhou) into, be mixed with the tio_2 suspension of 50g/L, and with vinegar acid for adjusting pH to 4.0, then high-speed stirring is disperseed 30min under hyperacoustic effect, follow the KH550(3-aminopropyl triethoxysilane with 10g/L), post-heating to 80 ℃ reaction 3h stirs; Then reaction product is filtered and with deionized water wash 3 times, at 100 ℃ of lower 12h of drying, at last products therefrom is ground into fine particle with pulverizer, namely get the modified manometer silicon dioxide catalyzer; Then with the modifying titanium dioxide catalyzer and the N that obtain, after the N N,N-DIMETHYLACETAMIDE mixes, after disperseing 30min under hyperacoustic effect, make the catalyzer suspension of 25g/L; In addition, in being full of the reactor of nitrogen, add vinyl acetic monomer and MDI, be heated to 40 ~ 50 ℃, after the dissolving, add the 0.05%(weight ratio that a small amount of sodium methylate and step b obtain fully) the catalyzer suspension; D, then slowly add TMP, the amount of this TMP be MDI weight 20%, behind 75 ℃ of lower reaction 3 ~ 4h, add a small amount of phosphoric acid at last, get final product.

Utilize MDI-TMP type polyurethane that above-mentioned nanometer titanium dioxide Si catalyst obtains to improve 90% with respect to the tensile strength of conventional polyurethanes, and the recovery of shape rate remain on more than 94%; Conventional polyurethanes is 7.7% through permanentset after 10 cyclic deformation processes, and this product then only is 3.5%.

Claims

1. elastic shape memory polyurethane is characterized in that making by following steps:

The preparation of a, catalyzer: get the nano titanium oxide suspension of 50g/L, and disperse 30min with vinegar acid for adjusting pH to 4.5 is rear with ultrasonic wave; Then add the KH550 of 10g/L, and increase the temperature to 80 ℃ of reaction 3h; At last reaction product is filtered, and use the deionized water wash post-drying, then be ground into fine particle, namely get the modifying titanium dioxide catalyzer;

B, with modifying titanium dioxide catalyzer and N that step a obtains, after the N N,N-DIMETHYLACETAMIDE mixes, under hyperacoustic effect, disperse to make the catalyzer suspension;

C, in being full of the reactor of nitrogen, add vinyl acetic monomer and MDI, be heated to 40 ~ 50 ℃, after the dissolving, add the catalyzer suspension that a small amount of sodium methylate and step b obtain fully;

D, then slowly add TMP, behind 75 ℃ of lower reaction 3 ~ 4h, add a small amount of phosphoric acid.

2. described elastic shape memory polyurethane according to claim 1, it is characterized in that: the content of modifying titanium dioxide catalyzer is 10 ~ 50g/L in the described catalyzer suspension of step b.

3. described elastic shape memory polyurethane according to claim 1, it is characterized in that: the weight ratio of described MDI and TMP is 2 ~ 5:1.