CN112662085A - Ultrahigh heat-resistant ABS material with excellent bonding strength with polyurethane and preparation method thereof - Google Patents

Abstract

The invention relates to the field of high polymer materials, in particular to an ultrahigh heat-resistant ABS material with excellent bonding strength with a polyurethane foam material, which comprises the following components in parts by weight: 20-40 parts of ABS resin, 50-70 parts of SAN resin, 1-10 parts of SMA resin, 1-10 parts of polyurethane, 0.1-5 parts of pumice, 0.1-1 part of antioxidant and 0.1-1 part of lubricant. The invention also provides a preparation method of the ultrahigh heat-resistant ABS material with excellent bonding strength with polyurethane. According to the invention, through adding pumice, on one hand, the effective surface area of the contact surface is improved, on the other hand, in the extrusion blending process, ABS resin containing polyurethane components can enter the pores of the pumice, and when the pumice is foamed and bonded with polyurethane, polyurethane foaming materials can also enter the pores or be bonded with materials in the pores, so that the bonding strength of the materials is further improved.

Description

Ultrahigh heat-resistant ABS material with excellent bonding strength with polyurethane and preparation method thereof

Technical Field

The invention relates to the field of high polymer materials, in particular to an ultrahigh heat-resistant ABS material with excellent bonding strength with polyurethane and a preparation method thereof.

Background

Polystyrene-butadiene-acrylonitrile (ABS for short) is an amorphous engineering plastic, has excellent toughness and processing fluidity, and is widely applied to automobile interior parts. Polyurethane (abbreviated as TPU) has excellent rebound resilience effect. Therefore, in some parts such as trims and armrests of high-grade vehicles, it is necessary to coat the ABS member with a polyurethane foam layer in order to improve the touch and appearance. And the compatibility of the conventional ABS and TPU is general, so that the preparation of the ABS material with excellent adhesion with polyurethane is particularly important.

Chinese patent document CN105367982A discloses a thermoplastic elastomer composition for bonding ABS and a preparation method thereof, which mainly achieves the purpose of bonding ABS by preparing a polyurethane resin, but the document achieves the bonding effect with polyurethane by adjusting ABS, and is substantially different from the present invention.

Chinese patent document CN104927336A discloses a PC/SMA material with resistance to wet heat aging and high PU foam bonding strength, which achieves the purpose of achieving high bonding strength with PU foam mainly by adding styrene-maleic anhydride copolymer (SMA) or SMA derivatives or any combination of the two.

However, no report is found about the ultra-high heat-resistant ABS material and the preparation method thereof, which can achieve excellent adhesion effect with polyurethane by ABS adjustment.

Disclosure of Invention

The invention aims to provide an ultrahigh heat-resistant ABS material with excellent bonding strength with polyurethane and a preparation method thereof, and solves the problem that the ABS material and a polyurethane foam material are easy to peel due to poor bonding strength.

The invention provides an ultrahigh heat-resistant ABS material with excellent bonding strength with polyurethane, which comprises the following components in parts by weight:

wherein the content of the first and second substances,

the weight average molecular weight of the ABS resin is 80000-150000 g/mol, and the ABS resin comprises 30-60 wt% of rubber, 10-30 wt% of acrylonitrile and 20-40 wt% of styrene. Specifically, ABS8391 of high petrochemical grade, H181 of Korea brocade lake, etc. can be selected.

The SAN resin has a molecular weight of 100,000-200,000g/mol and AN Acrylonitrile (AN) content of 26-37%. Specifically, Qimei PN-117C (acrylonitrile content: 26%), PN-127H (acrylonitrile content: 30%) and D-168 (acrylonitrile content: 35%) can be selected. The preferable content of acrylonitrile is 32-37%. More preferably D-168 having an acrylonitrile content of 35%.

The SMA resin is a copolymer of styrene and maleic anhydride, the weight-average molecular weight is 20,000-30,000g/mol, the glass transition temperature is 150-160 ℃, and the maleic anhydride content is more than or equal to 42%. In particular, SZ4005 (the content of maleic anhydride is 42%) of Polyscope can be selected.

The Shore hardness of the polyurethane resin is 50-90A. Specifically, WAIHUA WHT-1185EC of TTAIWANHUA can be selected, and the Shore hardness is 85A.

The pumice is white powder, the porosity is more than or equal to 60%, and the particle size is 0.1-3 mm. Pumice powder with a porosity of 70% is preferred. Specifically, YS-FS pumice of a Yu Chong water supply and drainage equipment factory in the city can be selected, the porosity is 70%, and the particle size is 0.5-1.5 mm.

The antioxidant is one or two of phosphite ester antioxidant 168, phosphite ester antioxidant S-9228, hindered phenol antioxidant 1010, hindered phenol antioxidant 1098 and hindered phenol antioxidant 1076.

The lubricant is one or more than two of silicone powder, pentaerythritol stearate and ethylene bisstearylamide.

In a preferred embodiment of the present invention, the ultra-high heat resistant ABS material with excellent adhesion strength to polyurethane comprises the following components in parts by weight:

wherein the selected ABS resin is HR181 of Korea brocade lake;

the selected SAN resin is Qimei D-168, and the content of acrylonitrile is 35 percent;

the selected SMA resin is SZ40005 of Polyscope, and the content of maleic anhydride is 42%;

the selected polyurethane resin is WHT-1185EC of Tantaowu, and the Shore hardness is 85A;

the pumice selected is YS-FS pumice from Yu Chong water supply and drainage equipment factories in consolidated city, the porosity is 70 percent, and the particle size is 0.5-1.5 mm;

the selected antioxidant is antioxidant 1098 and antioxidant 168 produced by CIBA company for compound use, and the weight ratio is 1: 1;

the lubricant selected is pentaerythritol stearate (PETS).

In a second aspect of the present invention, there is provided a method for preparing an ultra-high heat resistant ABS material having excellent adhesion strength with polyurethane as described above, comprising the steps of:

s1, preparing raw materials according to the weight part ratio, putting the raw materials into a premixer to uniformly mix the raw materials, heating the raw materials to 60 ℃, and then preserving the heat for 15 minutes to obtain a premix;

s2, adding the premix obtained in the step S1 into a double-screw extruder, extruding and pelletizing to obtain the PC/ABS composite material, wherein the rotating speed of a charging barrel of the double-screw extruder is 15-35rpm, and the temperature of the charging barrel is 220-;

s3, injection molding the PC/ABS composite material prepared in the step S2 to obtain a finished product.

The invention has the beneficial effects that:

according to the invention, the pumice is mainly added, on one hand, after blending modification, an uneven form is formed on the surface, and when the pumice modified polyurethane foam layer is combined with a polyurethane foam layer, the effective surface area of a contact surface is increased. On the other hand, pumice is mineral powder having a porous structure, and ABS resin containing a polyurethane component can enter pores during extrusion blending. When the polyurethane foaming adhesive is used for foaming and bonding with polyurethane, the polyurethane foaming material can also enter pores or be bonded with materials in the pores, so that the bonding strength is further improved.

Detailed Description

The following examples are provided to illustrate specific embodiments of the present invention.

In the following examples and comparative examples, the following ingredients were used for each raw material:

the selected ABS resin is ABS8391 of high petrochemical industry and H181 of Korean brocade lake;

the selected SAN resin is PN-117C and D-168;

the SMA resins selected are SZ25010 (the content of maleic anhydride is 25%) and SZ40005 (the content of maleic anhydride is 42%) of Polyscope;

the selected polyurethane resin is WHT-1185EC of Tantaowu, and the Shore hardness is 85A;

the talc powder is MONDO M05SLC, and the median particle size is 2.2 um.

The pumice selected is YS-FS pumice from Yu Chong water supply and drainage equipment factories in consolidated city, the porosity is 70 percent, and the particle size is 0.5-1.5 mm; the selected zeolite is 915 of a Toronto mineral processing plant in Lingshui county, the porosity is 50%, and the particle size is 0.5-1.5 mm.

The selected antioxidant is antioxidant 1098 and antioxidant 168 produced by CIBA company for compound use;

the lubricant selected is Pentaerythritol Ester (PETS).

Comparative examples 1 to 3 and examples 1 to 12:

s1, preparing raw materials according to the weight part ratios in the table 1 and the table 2, putting the raw materials into a premixer to uniformly mix the raw materials, heating the raw materials to 60 ℃, and then preserving the heat for 15 minutes to obtain premix;

s2, adding the premix obtained in the step S1 into a double-screw extruder, extruding and pelletizing to obtain the PC/ABS composite material, wherein the rotating speed of a charging barrel of the double-screw extruder is 15-35rpm, and the temperature of the charging barrel is 220-;

s3, carrying out injection molding on the ABS composite material prepared in the step S2 to obtain a finished product.

TABLE 1 raw Material compositions for comparative examples 1 to 3 and examples 1 to 4

TABLE 2 raw material compositions of examples 5 to 12

Example 13: evaluation of the effects of the implementations

The materials prepared in comparative examples 1 to 3 and examples 1 to 12 were subjected to the relevant tests. Melt index was tested according to ISO 1133; flexural strength was tested according to ISO 178; the notched impact strength is tested according to ISO 179-1; the bonding strength was measured by cutting a sample obtained by bonding ABS and polyurethane into a tensile sample, and cutting the sample to separate the polyurethane from the ABS. The test results are shown in tables 3 and 4.

TABLE 3 Performance evaluation and implementation criteria for comparative examples 1-3 and examples 1-5

TABLE 4 evaluation of Performance and implementation criteria for examples 6-12

As can be seen from comparative examples 1 and 2, the use of D-168 has better bond strength than PN-117C. This is because D-168 (with AN content of 35%) has a higher AN content than PN-117C (with AN content of 26%), the higher the AN content, the more polar the material. Since polyurethane itself is also a polar material, the adhesion is higher.

As can be seen from the comparative example 2 and the examples 1 to 4, the compatibility of the polyurethane foaming layer can be improved by adding the polyurethane WHT-1185EC into the ABS, so that the bonding strength is improved. However, the vicat softening temperature and the flexural strength gradually decrease as the addition amount gradually increases. It can be seen from comparative example 3, example 6 and example 12 that with the addition of SMA, the bond strength with the polyurethane foam layer is significantly improved because SMA is very compatible with both SAN and polyurethane. In addition, when the content of the maleic anhydride in the SMA is increased from 25% to 42%, the adhesion with the polyurethane foam layer is also remarkably improved, because the maleic anhydride is a main influence factor for improving the compatibility between the SAN and the polyurethane. The higher the maleic anhydride content, the better the reactivity is relatively. When the content of the maleic anhydride reaches 42%, the effect is better.

From examples 6 and 11, it can be seen that the use of 70% porosity of pumice YS-FS has better adhesion than the use of 915 zeolite with 50% porosity, since the higher the porosity, the more ABS resin is absorbed in the voids, which is more favorable for the improvement of adhesion. As can be seen from examples 3 and 5 to 7, the bonding strength is obviously improved with the addition of pumice. This is because pumice is a porous mineral powder and the porosity reaches 70%. Therefore, on one hand, the surface area is increased when the polyurethane foam layer is bonded; on the other hand, during blending, the ABS resin may enter into the voids of the pumice stone. When peeling occurs, the resin in the voids is more difficult to peel off, and the adhesive strength with the polyurethane foam layer is improved. However, as the amount of pumice added is further increased, the impact strength of the product is reduced. The best solution is shown in example 6.

While the preferred embodiments of the present invention have been described in detail, it will be understood by those skilled in the art that the invention is not limited thereto, and that various changes and modifications may be made without departing from the spirit of the invention, and the scope of the appended claims is to be accorded the full range of equivalents.

Claims (10)

1. The ultrahigh heat-resistant ABS material with excellent bonding strength with polyurethane is characterized by comprising the following components in parts by weight:

2. the ABS material having excellent adhesion strength with polyurethane according to claim 1, wherein the weight average molecular weight of the ABS resin is 80000-150000 g/mol, and the ABS resin comprises 30-60 wt% of rubber, 10-30 wt% of acrylonitrile, and 20-40 wt% of styrene.

3. The ABS material having excellent adhesive strength with polyurethane as claimed in claim 1, wherein the SAN resin has a molecular weight of 100,000-200,000g/mol and an acrylonitrile content of 26-37%.

4. The ABS material with excellent adhesion strength to polyurethane as claimed in claim 1, wherein the SMA resin is a copolymer of styrene and maleic anhydride, and has a weight average molecular weight of 20,000-30,000g/mol, a glass transition temperature of 150-160 ℃, and a maleic anhydride content of 42% or more.

5. The ABS material having excellent adhesion to polyurethane according to claim 1, wherein the shore hardness of the polyurethane resin is 50A to 90A.

6. The ABS material with excellent bonding strength with polyurethane as claimed in claim 1, wherein the pumice is white powder, the porosity is not less than 60%, and the particle size is 0.1-3 mm.

7. The ABS material with excellent bonding strength with polyurethane as claimed in claim 1, wherein the antioxidant is one or two of phosphite antioxidant 168, phosphite antioxidant S-9228, hindered phenol antioxidant 1010, hindered phenol antioxidant 1098 and hindered phenol antioxidant 1076.

8. The ABS material having excellent adhesion strength with polyurethane according to claim 1, wherein the lubricant is one or more selected from silicone powder, pentaerythritol stearate, and ethylene bisstearamide.

9. The ABS material with excellent bonding strength with polyurethane as claimed in claim 1, wherein the ABS material comprises the following components in parts by weight:

10. a method for preparing an ultra-high heat resistant ABS material having excellent adhesive strength with polyurethane according to any one of claims 1 to 9, comprising the steps of:

s1, preparing raw materials according to the weight part ratio, putting the raw materials into a premixer to uniformly mix the raw materials, heating the raw materials to 60 ℃, and then preserving the heat for 15 minutes to obtain a premix;

s2, adding the premix obtained in the step S1 into a double-screw extruder, extruding and pelletizing to obtain the PC/ABS composite material, wherein the rotating speed of a charging barrel of the double-screw extruder is 15-35rpm, and the temperature of the charging barrel is 220-;

s3, injection molding the PC/ABS composite material prepared in the step S2 to obtain a finished product.