阅读说明：本技术 一种可交联的tpu组合物及其制备方法 (A kind of crosslinkable TPU composition and preparation method thereof ) 是由 周小三 于 2019-08-07 设计创作，主要内容包括：本发明提供了一种可在高温下可交联的TPU组合物及其制备方法,该组合物包括环氧封端的TPU和引发剂,其中,所述环氧封端的TPU是在TPU链端含有环氧基团。本发明通过在TPU分子链的链端引入可交联的基团,同时混入高温引发剂得到的TPU组合物进行加工时,高温会使得引发剂引发交联基团进行交联,从而实现TPU制品优异性能。(It can crosslinkable TPU composition and preparation method thereof, the composition include at high temperature epoxy-capped TPU and initiator the present invention provides one kind, wherein the epoxy-capped TPU is to contain epoxy group in the TPU end of the chain.The present invention introduces crosslinkable group by the end of the chain in TPU strand, while when being mixed into the TPU composition that high-temperature initiator obtains and being processed, and high temperature can initiator cause crosslinked group to be crosslinked, to realize TPU product excellent properties.)

1. a kind of crosslinkable TPU composition, wherein the composition includes epoxy-capped TPU and initiator, wherein institute Stating epoxy-capped TPU is to contain epoxy group in the TPU end of the chain.

2. composition according to claim 1, wherein the epoxy-capped TPU is by TPU in the molten state It is reacted with epoxy prapanol.

3. composition according to claim 1, wherein the epoxy-capped TPU has a structure that

。

4. composition according to claim 1, wherein the initiator is cationic initiator.

5. composition according to claim 4, wherein the cationic initiator is hexafluoro antimonate.

6. the preparation method of composition according to claim 1, the described method comprises the following steps:

(1) it polymerize preparation TPU according to typical high-temperature fusant, wherein keeping isocyanates excessive；

(2) under nitrogen protection, and temperature be greater than TPU fusing point when in the case where being stirred in step (1) TPU obtained Middle epoxy group of the addition containing hydroxyl is stirred continuously until that detection NCO reaches theoretical value, epoxy-capped TPU is made；

(3) epoxy-capped TPU obtained in step (2) is mixed with initiator and carries out cross-linking reaction, TPU composition is made.

7. the preparation method of composition according to claim 1, the described method comprises the following steps:

(1) it polymerize preparation TPU according to typical high-temperature fusant, wherein keeping isocyanates excessive；

(2) under nitrogen protection and temperature be greater than TPU fusing point when, in the case where being stirred in step (1) TPU obtained Middle addition epoxy prapanol is stirred continuously until that detection NCO reaches theoretical value, so that epoxy-capped TPU be made；

(3) epoxy-capped TPU obtained in step (2) is mixed with hexafluoro antimonate at 80-250 DEG C and carries out cross-linking reaction, To obtain TPU composition.

8. the preparation method of composition according to claim 6 or 7, wherein wherein the epoxy-capped TPU have with Flowering structure:

。

Technical field

The present invention relates to a kind of crosslinkable TPU compositions and preparation method thereof.

Technical background

In recent years, with the development of society and advancement of technology, new diseases are more and more extensive, thermoplastic polyurethane Elastomer (TPU) since the beginning of the eighties in last century start from it is military switch to it is dual-use, and based on civilian after, the product of product The kind trade mark is continuously increased, and production scale is growing, and is played in the clothing, food, lodging and transportion -- basic necessities of life various aspects of each department of national economy and people Effect it is increasingly important.

Since TPU has linear molecular structure, in performances such as high temperature resistant, solvent resistant, wearability and imperfect, so And to be exactly TPU much necessarily required using field the performances such as wearability, solvent resistant, such as aircraft or naval vessel surface Protection, the TPU protective film of wind blade and car surface paint, it is necessary to have good wearability.

Crosslinking (solidification) type TPU has become one of the hot spot direction of TPU research, however these study generally concentrate on by Unsaturated bond such as double bond introduces TPU, is then crosslinked by crosslinking methods such as UV or electron radiations, however UV or electronics spoke Penetrate crosslinking all has certain injury to TPU, and these require additional initiation source such as UV, electron radiation etc..

It is crosslinked therefore, it is necessary to develop the completely new crosslinking method of one kind, and does not injure TPU.

Summary of the invention

In order to overcome defect present in existing crosslinking technological, technical scheme is as follows:

The present invention provides a kind of crosslinkable TPU compositions, wherein the composition include epoxy-capped TPU and Initiator, wherein the epoxy-capped TPU is to contain epoxy group in the TPU end of the chain.

In a preferred embodiment of the present invention, the epoxy-capped TPU be by TPU in the molten state with What epoxy prapanol reacted.

In a preferred embodiment of the present invention, wherein the epoxy-capped TPU has a structure that

。

In a preferred embodiment of the present invention, wherein the initiator is cationic initiator.

In a preferred embodiment of the present invention, wherein the cationic initiator is hexafluoro antimonate.

The present invention also provides a kind of preparation methods of composition, the described method comprises the following steps:

(1) it polymerize preparation TPU according to typical high-temperature fusant, wherein keeping isocyanates excessive；

(2) under nitrogen protection, it is made in the case where being stirred in step (1) when and temperature is greater than TPU fusing point TPU in be added the epoxy group containing hydroxyl, be stirred continuously until detection NCO reach theoretical value, be made epoxy-capped TPU；

(3) epoxy-capped TPU obtained in step (2) is mixed with initiator and carries out cross-linking reaction, TPU combination is made Object.

The present invention also provides a kind of preparation methods of composition, the described method comprises the following steps:

(1) it polymerize preparation TPU according to typical high-temperature fusant, wherein keeping isocyanates excessive；

(2) under nitrogen protection and temperature be greater than TPU fusing point when, in the case where being stirred in step (1) be made TPU in epoxy prapanol is added, be stirred continuously until detection NCO reach theoretical value, so that epoxy-capped TPU be made；

(3) epoxy-capped TPU obtained in step (2) is mixed with hexafluoro antimonate at 80-250 DEG C and be crosslinked instead It answers, to obtain TPU composition.

In a preferred embodiment of the present invention, wherein wherein the epoxy-capped TPU has a structure that

。

Specific embodiment

The technical problem to be solved by the present invention is to prepare the TPU for having crosslinkable groups, while finding under a kind of high temperature The initiator of the crosslinked group can be caused, so that the TPU is crosslinked rapidly to realize TPU product excellent properties at high temperature.Together When TPU molecular weight usually very high (MW is greater than 100,000) cause TPU fluidity of molten poor in this way, processing difficulties.Therefore it is reducing Introducing crosslinked group while TPU molecular weight is conducive to improve the above performance.In order to achieve the object of the present invention, of the invention Technical solution is as follows:

The present invention provides a kind of crosslinkable TPU compositions, wherein the composition include epoxy-capped TPU and Initiator, wherein the epoxy-capped TPU is to contain epoxy group in the TPU end of the chain.The initiator at high temperature may be used simultaneously To cause cross-linking reaction.High temperature refers to that temperature is 80~250 DEG C.

In a preferred embodiment of the present invention, the epoxy-capped TPU be by TPU in the molten state with What epoxy prapanol reacted.

In a preferred embodiment of the present invention, wherein the epoxy-capped TPU has a structure that

。

In a preferred embodiment of the present invention, wherein the initiator is cationic initiator.

In a preferred embodiment of the present invention, wherein the cationic initiator is hexafluoro antimonate.

The present invention also provides a kind of preparation methods of composition, the described method comprises the following steps:

(1) TPU (i.e. end group contain isocyanate groups TPU) is prepared according to the polymerization of typical high-temperature fusant, wherein protecting Hold isocyanates excess；

(2) under nitrogen protection, when and temperature is greater than TPU fusing point (in the molten state) in the case where being stirred The epoxy group containing hydroxyl is added in TPU obtained in step (1), is stirred continuously until that detection NCO reaches theoretical value, Epoxy-capped TPU is made；

(3) epoxy-capped TPU obtained in step (2) is mixed with initiator and carries out cross-linking reaction, TPU combination is made Object.

The present invention also provides a kind of preparation methods of composition, the described method comprises the following steps:

(1) TPU (i.e. end group contain isocyanate groups TPU) is prepared according to the polymerization of typical high-temperature fusant, wherein protecting Hold isocyanates excess；

(2) under nitrogen protection and temperature be greater than TPU fusing point when (in the molten state), in the case where being stirred Epoxy prapanol is added in TPU obtained in step (1), is stirred continuously until that detection NCO reaches theoretical value, so that ring be made The TPU of oxygen sealing end；

(3) epoxy-capped TPU obtained in step (2) is mixed with hexafluoro antimonate at 80-250 DEG C and be crosslinked instead It answers, to obtain TPU composition.

In a preferred embodiment of the present invention, wherein wherein the epoxy-capped TPU has a structure that

。

The present invention is the crosslinkable group of end of the chain introducing in TPU strand, which includes aliphatic TPU and aromatic series TPU.The molecular weight of TPU can control 100,000 hereinafter, being mixed into high-temperature initiator simultaneously in this way.The TPU composition is processed When, high temperature can make initiator initiation crosslinked group be crosslinked.Crosslinkable groups of the invention are epoxy groups.

Epoxy-capped TPU in the present invention means that the end of the chain of TPU strand contains can crosslinkable epoxy at high temperature Group.

The typical high-temperature fusant polymerization process for preparing of TPU is as follows: methyl diphenylene diisocyanate (MDI) is heated to 80-240 DEG C DEG C, polyester polyol or polyether polyol are heated to 180-240 DEG C, Isosorbide-5-Nitrae butanediol (BDO) is heated to 100-240 DEG C, dynamic mixer or static mixer according to recipe requirements will be added by three kinds of materials above by metering system It carries out after quickly mixing, twin-screw granulating system is added in the material mixed and carries out reactive extrursion granulation to prepare The material mixed can also be placed on the conveyer belt of heating after being cured and be granulated that TPU is made by TPU.