WO2021114664A1

WO2021114664A1 - Polyurethane elastomer for manufacturing quick-demolding high temperature-resistant transparent model material and preparation method therefor

Info

Publication number: WO2021114664A1
Application number: PCT/CN2020/102538
Authority: WO
Inventors: 代金辉; 刘兆阳; 李英乾; 孙汉禄
Original assignee: 山东一诺威聚氨酯股份有限公司
Priority date: 2019-12-12
Filing date: 2020-07-17
Publication date: 2021-06-17
Also published as: CN110903457A

Abstract

A polyurethane elastomer for manufacturing a quick-demolding high temperature-resistant transparent model material and a preparation method therefor. The elastomer is prepared from a component A (a polymer component) and a component B (a prepolymer component), wherein the component A is prepared from polyether polyol, a plasticizer, a high temperature-resistant filler, a catalyst, an antioxidant, and an anti-ultraviolet absorbent; and the component B is prepared from diisocyanate and polyether polyol, and the NCO content of the component B is 18-30%. The polyurethane elastomer has the advantages of high mold opening speed, strong high-temperature resistance, good appearance transparency, molding by one-time casting, and no need for secondary casting; and the prepared model material has excellent comprehensive performance, can be used for industrial mass production of high-performance transparent model materials, and has great application prospects in the field of preparation of human body models, related roll molding products and the like. The preparation method therefor is scientific and reasonable, simple and feasible, and is easy for industrial production.

Description

Polyurethane elastomer used for making quick demoulding high temperature resistant transparent model material and preparation method thereof

Technical field

The invention belongs to the technical field of polyurethane applications, and in particular relates to a polyurethane elastomer used for making rapid demolding and high temperature resistant transparent model materials and a preparation method thereof.

Background technique

At present, the main materials of human clothing models are divided into three categories: one is processed by unsaturated polyester resin and glass fiber reinforced plastic, but there are disadvantages such as long production cycle, high pollution, and difficulty in subsequent processing of the product surface; second, through Polyvinyl chloride, polypropylene and other plastic materials are thermoformed, but there are also the problems of high energy consumption, large shrinkage, unstable structure and short service life in the early production. The third is the rotational molding of high-hardness polyurethane materials, which is compared with the previous two. The polyurethane model has the advantages of light weight, simple processing, excellent performance, long service life, adjustable hardness, etc. It is an excellent material to replace traditional glass fiber reinforced plastic models and plastic models.

However, the current use of polyurethane materials to produce human clothing models has disadvantages such as slow mold opening speed, poor high temperature resistance, not conducive to maritime transportation, the product requires secondary pouring of fillers, poor appearance transparency, and further color painting processing in the later stage, which limits the polyurethane elastomer Further applications in related manufacturing fields such as mannequins.

Summary of the invention

The technical problem to be solved by the present invention is to overcome the shortcomings of the prior art and provide a polyurethane elastomer used for making quick release and high temperature resistant transparent model material, which has fast mold opening speed, strong high temperature resistance and good appearance transparency. , The advantages of one-time casting without secondary casting, and the prepared model materials have excellent comprehensive properties, which can be used for industrial mass production of high-performance transparent model materials, and have huge applications in the preparation of mannequins and rotomolding related products; The invention also provides its preparation method, which is scientific and reasonable, simple and easy to implement, and easy for industrial production.

The polyurethane elastomer used in the present invention for making rapid demolding and high temperature resistant transparent model material is made of component A (polymer component) and component B (prepolymer component), in which:

In terms of weight percentage, component A is made from the following raw materials:

Polyether polyol 70-85%, plasticizer 5-15%, high-temperature filler 5-15%, catalyst 0.01-1.5%, antioxidant 0.2-1.5%, anti-ultraviolet absorber 0.1-1.0%;

In terms of weight percentage, component B is made from the following raw materials:

Diisocyanate 35～80%, polyether polyol 20～65%;

The cyanate ester group (NCO) content of component B is 18-30%.

among them:

In component A, the content of polyether polyol can be reasonably adjusted within the above range according to the performance of the required product, for example, it can be 50%, 70%, 90%, etc.; the content of catalyst in component A can be It can be selected within the above range according to the actual reaction needs, for example, it can be 0.01%, 0.5%, 1.0%, etc.; the content of antioxidant in the A component can be selected within the above range according to the actual reaction needs, for example, It is 0.25%, 0.9%, 1.0%, etc.

In component A, the polyether polyol is a polyether polyol with a functionality of 4 to 5 organs and a number average molecular weight of 200 to 4000 and a polyether with a functionality of 2 to 3 organs and a number average molecular weight of 300 to 6000. Mixtures in polyols.

The polyether polyol with a functionality of 4 to 5 guanosity and a number average molecular weight of 200 to 4000 is one or more of INOVOL R8345, NJ6209 or INOVOL R5118G, preferably INOVOL R8345 or NJ6209.

The polyether polyol with a functionality of 2 to 3 and a number average molecular weight of 300 to 6000 is one or more of DL-400, EP-330NG, MN3050, DL-1000, EP-3600 or DV125, preferably DL- 1000, DL-400, EP-3600 or DV125.

In component A, the plasticizer is one or a mixture of dioctyl terephthalate, dioctyl adipate, dioctyl sebacate or acetyl tributyl citrate .

In component A, the high temperature resistant filler is one or a mixture of mica powder, natural aluminosilicate or vacuum glass beads.

In component A, the catalyst is one or a mixture of organic tin catalysts, organic bismuth catalysts or organic amine catalysts. The organic tin catalyst is preferably dibutyltin dilaurate and stannous octoate; the organic bismuth catalyst is preferably bismuth isooctanoate, bismuth laurate, and bismuth naphthenate; the organic amine catalyst is preferably triethylenediamine and triethylamine.

In component A, the antioxidant is antioxidant 1070 (β-(3,5-di-tert-butyl-4-hydroxyphenyl) stearyl propionate), antioxidant 1010 (tetra[β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid) pentaerythritol ester) or antioxidant 1098 (N,N'-1,6-hexylene-bis[3-(3,5- One or a mixture of one or more of di-tert-butyl-4-hydroxyphenyl)propionamide), preferably antioxidant 1070, and the amount is preferably 0.5%.

In component A, the anti-ultraviolet absorber is anti-ultraviolet absorber 328 (2-(2'-hydroxyphenyl 3',5'-dipentylphenyl) benzotriazole), anti-ultraviolet absorber One of 329 (2-(2-hydroxy-5-tert-octylphenyl)benzotriazole) or UV-531 (2-hydroxy-4-n-octyloxybenzophenone) Or a mixture of several, preferably UV absorber 328, and the amount is preferably 0.3%.

In component B, the content of diisocyanate can be reasonably adjusted within the above range according to actual needs, for example, it can be 36%, 45%, 75%, etc.; the content of polyether polyol in component B can be adjusted according to It needs to be adjusted reasonably within the above range, for example, it can be 25%, 40%, 60%, and so on.

In component B, the diisocyanate is toluene diisocyanate (MDI-100), carbonized diimide modified diphenylmethane diisocyanate (liquefied MDI), HDI trimer, isophorone diisocyanate or One or a mixture of methylene diphenyl diisocyanate.

In component B, the polyether polyol is one or a mixture of DL-400, DL-1000, EP-330NG or EP-3600.

The preparation method of the polyurethane elastomer used for making rapid demoulding and high temperature resistant transparent model material of the present invention includes the following steps:

(1) Preparation of component A:

It is prepared by mixing polyether polyol, plasticizer, antioxidant, anti-ultraviolet absorber, catalyst and high temperature resistant filler uniformly, and vacuum dehydration at 100-120℃;

(2) Preparation of component B:

After the polyether polyol is vacuum dehydrated to a moisture content of less than 0.05%, it is cooled to below 60°C, the isocyanate is added under stirring, the temperature is raised to 75-85°C, and the temperature is kept. After passing the test, it is flushed into nitrogen and sealed for storage.

In step (1), the dehydration vacuum degree is preferably 0.09MPa, the dehydration time is preferably 1-2h, and the moisture content is ≤0.05%.

In step (2), the reaction temperature can be adjusted within the above range according to the reaction situation, and can also be 76°C, 82°C, 85°C, and the like.

When used, the mass ratio of component A to component B is A:B=60-100:100. When using the polyurethane elastomer of the present invention to prepare a product, the A component and the B component are mixed at a ratio of A:B=60-100:100 at 30°C at room temperature. After stirring, they are poured to 30°C. In the rotational molding mold at -40°C, horizontal and vertical rotation and leveling are performed at the same time, the swing is stopped for 3-5 minutes, and the mold is opened after 10-15 minutes to obtain the target product.

Compared with the prior art, the present invention has the following beneficial effects:

1. The high-performance polyurethane elastomer used in the present invention for preparing rapid demoulding and high-temperature resistant transparent molding materials, through the co-catalysis of high-activity special polyether and selected catalysts in the A component, the elastomer has The advantages of fast mold opening speed and no need for secondary casting in one-time casting. At the same time, component A is added with high-temperature resistant fillers and polyether polyols with appropriate high functionality, combined with a prepolymer component synthesized by aliphatic isocyanate in component B , The prepared model material has good transparency and excellent comprehensive performance, and can be used for industrial mass production of high-performance transparent model materials.

2. The high-performance polyurethane elastomer of the present invention has a simple preparation process, a short cycle, and almost no pollution, is suitable for industrial production, and has great applications in the preparation of mannequins and rotomolding related products.

Detailed ways

The present invention will be further described below in conjunction with embodiments, but they do not limit the implementation of the present invention.

The materials used are as follows:

INOVOL R8345: a polyether polyol with a functionality of 4 and a number average molecular weight of 500;

EP-330NG: a polyether polyol with a functionality of 3 and a number average molecular weight of 5000;

EP-3600: a polyether polyol with a functionality of 3 and a number average molecular weight of 6000;

DV125: a polyether polyol with a functionality of 3 and a number average molecular weight of 375;

DL-1000: A polyether polyol with a functionality of 2, and a number average molecular weight of 1000;

DL-400: A polyether polyol with a functionality of 2, and a number average molecular weight of 400;

IPDI: isophorone diisocyanate;

MDI-100: 4,4'-diphenylmethane diisocyanate;

MM103C: MDI-100 modified with carbodiimide.

The raw materials used in the examples are all commercially available materials except those already described above.

In the examples, component A and component B are calculated according to mass percentages.

Example 1

The formulation of the polyurethane elastomer used to make the rapid demoulding and high temperature resistant transparent model material and the preparation method thereof are as follows:

Component A: DL-400 15%, INOVOL R8345 50%, EP-330NG 19%, dioctyl adipate 10%, high temperature filler natural aluminosilicate transparent powder 5%, bismuth laurate 0.2%, antioxidant 1098 0.5%, UV absorber 328, 0.3%, the above components are mixed uniformly, heated to 110°C and vacuum dehydrated until the moisture content is below 0.05%.

Component B: DL-400 20%, IPDI 24%, MM103C 56%, reacted at 80°C for 3 hours to obtain a prepolymer with an isocyanate content of 21%.

The temperature of component A and component B is normal temperature, and they are mixed at 30℃ according to the mass ratio of A:B=100:100. After stirring evenly, they are poured into a rotomoulding mold at 40℃, and the vertical and horizontal three-dimensional shapes are carried out at the same time. Rotate and open the mold for 15 minutes to obtain the product. The results are shown in Table 1.

Example 2

Component A: INOVOL R8345 15%, DV125 45%, EP-3600 20%, dioctyl adipate 10%, high temperature filler natural aluminosilicate transparent powder 9%, stannous octoate 0.1%, bismuth laurate 0.1 %, antioxidant 1098 0.3%, antioxidant 1070 0.2%, ultraviolet absorber 328 0.3%, the above components are evenly mixed, heated to 110°C and vacuum dehydrated to a moisture content of less than 0.05%.

Component B: DL-1000 38%, MDI-100 33%, IPDI 29%, react at 75°C for 3 hours to obtain a prepolymer with an isocyanate content of 28%.

The temperature of component A and component B are at room temperature. They are mixed at 30°C according to the ratio of A:B=90:100. After stirring, they are poured into a 35°C rotomolding mold, and the vertical and horizontal three-dimensional rotations are carried out at the same time. Open the mold in minutes to get the product. The results are shown in Table 1.

Example 3

Component A: DV125 40%, INOVOL R8345 44%, dioctyl adipate 10%, mica powder 5%, stannous octoate 0.1%, bismuth isooctanoate 0.1%, antioxidant 1070 0.5%, ultraviolet absorber UV531, 0.3%, the above components are mixed uniformly, heated to 110°C and vacuum dehydrated until the moisture content is below 0.05%.

Component B: EP-330NG 25%, IPDI 53%, MDI-100 22%, reacted at 80°C for 3 hours to obtain a prepolymer with an isocyanate content of 27%.

The temperature of component A and component B is normal temperature. They are mixed at 30°C according to the ratio of A:B=95:100. After stirring, they are poured into a 30°C rotomolding mold, and the vertical and horizontal three-dimensional rotations are carried out at the same time. The mold was opened in 12 minutes to obtain the product. The results are shown in Table 1.

Example 4

Component A: DV125 30%, INOVOL R8345 40%, DL-1000 19%, dioctyl terephthalate 5%, high-temperature filler natural aluminosilicate transparent powder 5%, stannous octoate 0.2%, antioxidant 1070 0.5%, ultraviolet absorber UV531, 0.3%, the above components are mixed uniformly, heated to 110°C and vacuum dehydrated until the moisture content is below 0.05%.

Component B: DL-400 20%, MDI-100 24%, MM103C 56%, react at 80°C for 3 hours to obtain a prepolymer with an isocyanate content of 20%.

The temperature of component A and component B is normal temperature. They are mixed at 30°C according to the ratio of A:B=80:100, stirred evenly and poured into a 35°C rotomolding mold, while performing vertical and horizontal three-dimensional rotations. The mold was opened in 14 minutes to obtain the product. The results are shown in Table 1.

Example 5

A component: INOVOL R8345 20%, DV125 35%, EP-3600 24%, dioctyl adipate 10%, high temperature filler natural aluminosilicate transparent powder 10%, triethylene diamine 0.2%, stannous octoate 0.2%, antioxidant 1098, 0.3%, ultraviolet absorber 328, 0.3%, the above components are mixed uniformly, heated to 110°C and vacuum dehydrated until the moisture content is below 0.05%.

Component B: DL-1000 35%, MDI-100 43%, IPDI 22%, react at 80°C for 3 hours to obtain a prepolymer with an isocyanate content of 25%.

The temperature of component A and component B is at room temperature. They are mixed at 30°C according to the ratio of A:B=100:100. After stirring, they are poured into a rotomoulding mold at 40°C. The vertical and horizontal three-dimensional rotations are carried out at the same time. Open the mold in minutes to get the product. The results are shown in Table 1.

Example 6

Component A: DV125 25%, INOVOL R8345 44%, EP-330NG 15%, acetyl tributyl citrate 10%, high-temperature filler natural aluminosilicate transparent powder 5%, triethylene diamine 0.2%, subcaprylic acid Tin 0.2%, antioxidant 1070 0.3%, ultraviolet absorber 328, 0.3%, the above components are mixed uniformly, heated to 110°C and vacuum dehydrated until the moisture content is below 0.05%.

Component B: EP-330NG 30%, MDI-100 49%, IPDI 21%, react at 80°C for 3 hours to obtain a prepolymer with an isocyanate content of 22%.

The temperature of component A and component B is normal temperature, and they are mixed under the condition of 30℃ according to the ratio of A:B=100:100. After stirring, they are poured into a 35℃ rotomoulding mold, and the vertical and horizontal three-dimensional rotation are carried out at the same time. , 10 minutes to open the mold to get the product. The results are shown in Table 1.

Table 1 Example 1-6 performance index parameter data table

The mold opening hardness, final hardness, and 60℃ high temperature hardness are all measured in accordance with the GB/T 531.1-2008 standard.

The transparency rate is measured in accordance with the GB/T 2410-2008 standard.

Claims

A polyurethane elastomer used for making quick demoulding and high temperature resistant transparent model material, which is characterized in that it is made of A component and B component, in which:

In terms of weight percentage, component A is made from the following raw materials:

Polyether polyol 70-85%, plasticizer 5-15%, high-temperature filler 5-15%, catalyst 0.01-1.5%, antioxidant 0.2-1.5%, anti-ultraviolet absorber 0.1-1.0%;

In terms of weight percentage, component B is made from the following raw materials:

Diisocyanate 35～80%, polyether polyol 20～65%;

The cyanate ester group content of component B is 18-30%.
The polyurethane elastomer for making quick-release and high-temperature resistant transparent model materials according to claim 1, characterized in that: in the A component, the polyether polyol has a functionality of 4 to 5 organs and a number average A mixture of a polyether polyol with a molecular weight of 200 to 4000 and a polyether polyol with a functionality of 2 to 3 and a number average molecular weight of 300 to 6000.
The polyurethane elastomer for making quick-release and high-temperature-resistant transparent model materials according to claim 1, characterized in that: in the A component, the plasticizer is dioctyl terephthalate, adipic acid One or a mixture of dioctyl ester, dioctyl sebacate or acetyl tributyl citrate.
The polyurethane elastomer used for making quick release high temperature resistant transparent model material according to claim 1, characterized in that: in the A component, the high temperature resistant filler is mica powder, natural aluminosilicate or vacuum glass One or a mixture of several microbeads.
The polyurethane elastomer for making quick-release high-temperature resistant transparent model material according to claim 1, wherein in component A, the catalyst is an organotin catalyst, an organic bismuth catalyst or an organic amine One or a mixture of several catalysts.
The polyurethane elastomer used for making quick release high temperature resistant transparent model material according to claim 1, characterized in that: in the A component, the antioxidant is antioxidant 1070, antioxidant 1010 or antioxidant 1098 One or a mixture of several.
The polyurethane elastomer used for making quick release high temperature resistant transparent model material according to claim 1, characterized in that: in component A, the anti-ultraviolet absorber is anti-ultraviolet absorber 328 and anti-ultraviolet absorber 329 or anti-ultraviolet absorber UV-531 one or a mixture of several.
The polyurethane elastomer used for making quick release and high temperature resistant transparent model material according to claim 1, characterized in that: in the B component, the diisocyanate is toluene diisocyanate, carbonized diimide modified diisocyanate One or a mixture of phenylmethane diisocyanate, HDI trimer, isophorone diisocyanate or methylene diphenyl diisocyanate.
The polyurethane elastomer used for making quick release and high temperature resistant transparent model material according to claim 1, characterized in that: in the B component, the polyether polyol is DL-400, DL-1000, EP- One or a mixture of 330NG or EP-3600.
A method for preparing a polyurethane elastomer used for making quick release and high temperature resistant transparent model material according to any one of claims 1-9, characterized in that it comprises the following steps:

(1) Preparation of component A:

It is prepared by mixing polyether polyol, plasticizer, antioxidant, anti-ultraviolet absorber, catalyst and high temperature resistant filler uniformly, and vacuum dehydrating at 100～120℃;

(2) Preparation of component B:

After the polyether polyol is vacuum dehydrated to a moisture content of less than 0.05%, it is cooled to below 60°C, the isocyanate is added under stirring, the temperature is raised to 75-85°C, and the temperature is kept. After the test is qualified, it is flushed into nitrogen and sealed for storage;

(3) When used, the mass ratio of component A to component B is A:B=60-100:100.