阅读说明：本技术 发泡组合物 (Foaming composition ) 是由 张新玉 陈其 于 2017-12-22 设计创作，主要内容包括：本发明涉及一种发泡组合物,其包含至少一种乙烯-乙酸乙烯酯(EVA)共聚物；至少一种发泡剂；至少一种过氧化物化合物；至少一种多胺；至少一种交联促进剂；至少一种主抗氧化剂；和至少一种辅助抗氧化剂；所述交联促进剂的含量为基于该组合物总重量的0.1重量％至3重量％。根据本发明通过在80℃至120℃的温度范围内固化所述发泡组合物而制得的发泡制品在130℃至200℃的烘烤窗口显示出高的初始体积膨胀率,并且在储存后显示出优异的稳定性。(The present invention relates to a foaming composition comprising at least one ethylene-vinyl acetate (EVA) copolymer; at least one blowing agent; at least one peroxide compound; at least one polyamine; at least one crosslinking promoter; at least one primary antioxidant; and at least one secondary antioxidant; the content of the crosslinking accelerator is 0.1 to 3% by weight based on the total weight of the composition. The foamed article prepared by curing the foaming composition in a temperature range of 80 ℃ to 120 ℃ according to the present invention shows a high initial volume expansion rate in a baking window of 130 ℃ to 200 ℃ and excellent stability after storage.)

1. A foaming composition comprising:

(a) at least one Ethylene Vinyl Acetate (EVA) copolymer;

(b) at least one blowing agent;

(c) at least one peroxide compound;

(d) at least one polyamine;

(e) at least one crosslinking promoter;

(f) at least one primary antioxidant; and

(g) at least one secondary antioxidant;

wherein the crosslinking accelerator is contained in an amount of 0.1 to 3 wt% based on the total weight of the composition.

2. The foaming composition of claim 1 wherein the blowing agent is selected from the group consisting of 4, 4' -oxybis (benzenesulfonylhydrazide), azodicarbonamide, diisopropyl azodicarboxylate, and any combination thereof.

3. The foaming composition according to claim 1 or 2, wherein the peroxide compound is an organic peroxide compound and preferably is selected from the group consisting of 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, t-butylperoxybenzoate, benzoyl peroxide, di (t-butylperoxyisopropyl) benzene, dicumyl peroxide, 1-di- (t-butylperoxy) -3,3, 5-trimethylcyclohexane, butyl 4, 4-bis (t-butylperoxy) valerate and any combination thereof.

4. The foaming composition of any of the foregoing claims, wherein the polyamine is selected from the group consisting of diethyltoluenediamine, chlorodiaminobenzene, diethanolamine, diisopropanolamine, triethanolamine, tripropanolamine, 1, 6-hexanediamine, and any combination thereof.

5. The foaming composition of any of the preceding claims, wherein the crosslinking accelerator is selected from trimethylolpropane trimethacrylate, zinc diethyldithiocarbamate, di (morpholin-4-yl) disulfide, dipentamethylenethiuram tetrasulfide, and any combination thereof.

6. Foaming composition according to any of the previous claims, wherein the primary antioxidant is a phenolic antioxidant, preferably a hindered phenolic antioxidant.

7. The foaming composition of any of the previous claims, wherein the secondary antioxidant is selected from the group consisting of a phosphorous antioxidant, a sulfur antioxidant, and any combination thereof.

8. The foaming composition of any of the foregoing claims, further comprising an optional additive selected from at least one adhesion promoter, at least one filler, at least one lubricant, at least one wax, at least one dye, and any combination thereof.

9. The foaming composition of any of the foregoing claims comprising:

(a)45 to 70% by weight of at least one EVA copolymer;

(b)15 to 30 wt% of at least one blowing agent;

(c)0.1 to 10 wt% of at least one peroxide compound;

(d)0.001 to 2 wt% of at least one polyamine;

(e)0.1 to 3% by weight of at least one crosslinking promoter;

(f)0.04 to 10 wt.% of at least one primary antioxidant; and

(g)0.01 to 2 wt% of at least one secondary antioxidant;

wherein the weight percentages of all components add up to 100 wt.%, and the crosslinking facilitator is preferably present in an amount of from 1 wt.% to 2 wt.% of the total weight of the composition.

10. A foamed article made by curing the foamed composition of any preceding claim at a temperature of from 80 ℃ to 120 ℃, preferably from 95 ℃ to 105 ℃.

11. A foamed article prepared from the foamed composition of any of the preceding claims by:

a) mixing the components of the foaming composition at a temperature of 15 ℃ to 55 ℃ to form a homogeneous mixture;

b) granulating the homogeneous mixture by extrusion at a temperature of 90 ℃ to 100 ℃ to obtain foamed particles; and

c) forming the foamed article by injection molding the foamed particles at a temperature of 95 ℃ to 105 ℃.

12. The foamed article of claim 10 or 11, having a volume expansion change (Rc) of at least 5% after storage for 6 months at 40 ℃ and 50% RH and heating at a temperature of 140 ℃.

13. A foam article made from the foaming composition of any one of claims 1 to 9.

14. A foamed article made from the foamed article of any one of claims 10-12.

15. A vehicle comprising a vehicle component filled with the foam article of claim 13 or 14.

Technical Field

The present invention relates to a foaming composition comprising at least one ethylene-vinyl acetate (EVA) copolymer; at least one blowing agent; at least one peroxide compound; at least one polyamine; at least one crosslinking promoter; at least one primary antioxidant; and at least one secondary antioxidant; the content of the crosslinking accelerator is 0.1 to 3% by weight based on the total weight of the composition. The foamed article prepared by curing the foaming composition in the temperature range of 80 ℃ to 120 ℃ according to the present invention exhibits a high initial volume expansion rate in a baking window of 130 ℃ to 200 ℃ and excellent stability after storage.

Background

Foamed materials have been widely used in noise control applications in many areas of automotive, aircraft, and architectural acoustics.

In application to automobiles, a foamed article made of a foaming composition containing a foaming material such as an ethylene-vinyl acetate (EVA) copolymer is heated at a baking window of 160 ℃ to 200 ℃, generally according to the production line of automobiles. Foamed articles made from existing foaming compositions exhibit good volume expansion in current foaming processes. However, current toasting windows require high energy input and do not meet the global energy saving trend.

Therefore, there is a need to develop a foaming composition capable of sufficiently expanding at a low baking window temperature of 130 ℃ to 150 ℃ and a foamed article made of the foaming composition. It is desirable that the foamed article is also suitable for use in existing automotive production lines having a baking window of 160 ℃ to 200 ℃.

Disclosure of Invention

The present invention relates to a foaming composition comprising:

(a) at least one EVA copolymer;

(b) at least one blowing agent;

(c) at least one peroxide compound;

(d) at least one polyamine;

(e) at least one crosslinking promoter;

(f) at least one primary antioxidant; and

(g) at least one secondary antioxidant;

wherein the crosslinking accelerator is contained in an amount of 0.1 to 3 wt% based on the total weight of the composition.

Foamed articles made from the foamed composition exhibit high initial volume expansion at a bake window of 130 ℃ to 200 ℃ and excellent stability after 6 months of storage at 40 ℃ and 50% RH.

The invention also relates to a foamed article made by curing the foaming composition at a temperature in the range of 80 ℃ to 120 ℃, preferably in the range of 95 ℃ to 105 ℃.

The invention also relates to a foamed article made from the foamed composition by the steps of:

a) mixing the components of the foaming composition at a temperature of 15 ℃ to 55 ℃ to form a homogeneous mixture;

b) obtaining foamed particles by granulating the homogeneous mixture by extrusion at a temperature of 90 ℃ to 100 ℃; and

c) forming a foamed article from the foamed particles by injection molding at a temperature of 95 ℃ to 105 ℃.

The invention also relates to a foamed article made from the foamed composition.

The invention also relates to a foamed article made from the foamed article.

The invention also relates to a vehicle comprising a vehicle part filled with the foam article, wherein the vehicle part may be a pillar, a door or a body.

Detailed Description

In the following paragraphs, the present invention will be described in more detail. Each aspect described may be combined with any other aspect or aspects unless clearly indicated to the contrary. In particular, any feature indicated as being preferred or advantageous may be combined with any other feature or features indicated as being preferred or advantageous.

In the context of the present invention, the terms used will be construed according to the following definitions, unless the context indicates otherwise.

As used herein, the singular forms "a", "an" and "the" include both singular and plural referents unless the context clearly dictates otherwise.

As used herein, the terms "comprising" and "comprises" are synonymous with "including" or "containing" and are inclusive or open-ended and do not exclude additional unrecited members, elements or process steps.

The recitation of numerical endpoints includes all numbers and fractions within the respective range, as well as the recited endpoint.

All references cited in this specification are incorporated herein by reference in their entirety.

Unless defined otherwise, all terms used in disclosing the present invention, including technical and scientific terms, have the meaning commonly understood by one of ordinary skill in the art to which this invention belongs. By way of further guidance, definitions of terms are included to better understand the teachings of the present invention.

EVA copolymer

The EVA copolymer of the present invention refers to any common EVA copolymer, preferably having a Vinyl Acetate (VA) content of 12 wt% or more, and a melt index of 2-25g/10min at 190 ℃/2.16kg, more preferably having a VA content of 18 wt% to 30 wt%, and a melt index of 2.5-15g/10min at 190 ℃/2.16kg as measured by ASTM D1238.

Examples of commercially available EVA copolymers are, for example, Elvax 250 from Dupont; elvax 260 from Dupont; and Elvax 460 from Dupont.

In some embodiments of the invention, the amount of EVA copolymer in the foaming composition of the invention is from 45 to 70 wt%, preferably from 50 to 60 wt%, based on the total weight of the composition.

Foaming agent

The blowing agent of the present invention refers to any common blowing agent and may be selected from 4, 4' -oxybis (benzenesulfonylhydrazide) (OBSH), azodicarbonamide, diisopropyl azodicarboxylate, and any combination thereof.

In some embodiments of the invention, the blowing agent is preferably OBSH.

Examples of commercially available blowing agents are, for example, OBSH from IMCD Australia L imited, and OBSH from Western Reserve Chemical.

In some embodiments of the invention, the amount of blowing agent of the invention is from 15 to 30 weight percent, preferably from 20 to 25 weight percent, based on the total weight of the composition.

Peroxide compounds

The peroxide compound of the present invention refers to any common peroxide compound, preferably an organic peroxide. The peroxide compound is used as a crosslinking agent for crosslinking the EVA copolymer.

Examples of peroxide compounds include, but are not limited to, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, t-butyl peroxybenzoate, benzoyl peroxide, di (t-butylperoxyisopropyl) benzene, dicumyl peroxide, 1-di- (t-butylperoxy) -3,3, 5-trimethylcyclohexane, butyl 4, 4-bis (t-butylperoxy) valerate, and any combination thereof.

Examples of commercially available peroxide compounds are, for example, DCP40 from Arkema, and Varox 231X L from Vanderbilt Chemicals.

In some embodiments of the invention, the amount of peroxide compound is from 0.1 to 10 wt%, preferably from 0.2 to 6 wt%, more preferably from 1.5 to 3 wt%, based on the total weight of the composition.

Polyamine

The polyamine of the present invention refers to any common polyamine and is used as a crosslinking agent for crosslinking an EVA copolymer.

Examples of polyamines include, but are not limited to, diethyltoluenediamine, chlorodiaminobenzene (chlorodiaminobenzine), diethanolamine, diisopropanolamine, triethanolamine, tripropanolamine, 1, 6-hexanediamine, and any combination thereof.

Commercially available polyamines are, for example, Fujicure-FXR-1090FA from T & K Toka.

In some embodiments of the invention, the amount of polyamine is from 0.001 wt% to 2 wt%, preferably from 0.005 wt% to 0.5 wt%, based on the total weight of the composition.

Crosslinking accelerator

The crosslinking accelerator of the present invention means any common crosslinking accelerator capable of causing foaming at a relatively low temperature. Crosslinking accelerators include, but are not limited to, trimethylolpropane trimethacrylate, zinc diethyldithiocarbamate, di (morpholin-4-yl) disulfide (di (morpholino-4-yl) disulphide), dipentamethylenethiuram tetrasulfide, and any combination thereof.

Examples of commercially available crosslinking promoters are, for example, SR350 from Sartomer; and VISIOMER TMPTMA from Evonik.

In some embodiments of the invention, the amount of crosslinking promoter is from 0.1 to 3 wt%, preferably from 1 to 2 wt%, based on the total weight of the composition.

Primary antioxidant

The primary antioxidants of the present invention act as hydrogen atom donors in the conversion of peroxy radical oxidation intermediates to non-radical hydroperoxides and prevent degradation of the EVA copolymers. Preferably, the primary antioxidant is selected from the group consisting of aminic antioxidants, phenolic antioxidants, and any combination thereof.

In some embodiments of the present invention, the primary antioxidant is preferably a hindered phenolic antioxidant.

Examples of primary antioxidants include, but are not limited to, pentaerythrityl tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ], pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate ], octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 3 '-bis (3,5-di-tert-butyl-4-hydroxyphenyl) -N, N' -hexamethylenedipropionamide, and any combination thereof.

Examples of commercially available primary antioxidants are e.g. Irganox 1010 from Ciba, Irganox L107 from Ciba, and Irganox L109 from Ciba.

In some embodiments of the invention, the amount of primary antioxidant is from 0.04 to 10 wt%, preferably from 0.05 to 6 wt%, based on the total weight of the composition.

Secondary antioxidant

The secondary antioxidant of the present invention, unlike the primary antioxidant, is used in conjunction with the primary antioxidant to further remove the hydroperoxide so that the hydroperoxide does not decompose to form new initiating free radicals for oxidation. Preferably, the secondary antioxidant is selected from the group consisting of phosphorus-containing antioxidants, sulfur-containing antioxidants, and any combination thereof.

In some embodiments of the present invention, the secondary antioxidant is selected from the group consisting of phosphites, phosphonates, and any combination thereof.

Examples of secondary antioxidants include, but are not limited to, bis (2, 4-di-t-butylphenyl) pentaerythritol diphosphite, tris (2, 4-di-t-butylphenyl) phosphite, and combinations thereof.

Commercially available secondary antioxidants are for example Irgafos 168 from BASF.

In some embodiments of the invention, the amount of secondary antioxidant is from 0.01 to 2 wt%, preferably from 0.05 to 0.5 wt%, based on the total weight of the composition.

Other optional additives

In some embodiments of the present invention, the foaming composition may also optionally comprise other additives, such as at least one wax, at least one adhesion promoter, at least one filler, at least one lubricant, at least one dye, and any combination thereof.

In some embodiments of the present invention, the foaming composition may optionally comprise at least one wax. Preferably, the wax is a microcrystalline wax having a melting temperature of 90 ℃ to 100 ℃. Examples of commercially available waxes are, for example, Microere 5999A from International Group; and BE SQUARE 185Amber Wax available from Petrolite corporation.

In some embodiments of the present invention, the foaming composition may optionally include at least one adhesion promoter including, but not limited to, terpolymers of ethylene, acrylic esters, and maleic anhydride examples of commercially available adhesion promoters are Bondine HX 8290, available from Arkema, and L otaderBondine HX 8290 available from Arkema France INC.

In some embodiments of the present invention, the foaming composition may optionally include at least one filler, including but not limited to silica, mica, and Talc.

In some embodiments of the present invention, the foaming composition may optionally include at least one lubricant including, but not limited to, fatty alcohols and their dicarboxylic acid esters, fatty acid esters of short chain alcohols, fatty acids, fatty acid amides commercially available lubricants are, for example, stearic acid available from Changzhou Chemical Co., L TD.

In some embodiments of the present invention, the foaming composition may optionally include at least one dye. Preferably, the dye is carbon black. Commercially available dyes are e.g. Monarch 580 from Cabot corporation.

In a preferred embodiment, the foaming composition comprises:

(a)45 to 70% by weight of at least one EVA copolymer;

(b)15 to 30 wt% of at least one blowing agent;

(c)0.1 to 10 wt% of at least one peroxide compound;

(d)0.001 to 2 wt% of at least one polyamine;

(e)0.1 to 3% by weight of at least one crosslinking promoter;

(f)0.04 to 10 wt.% of at least one primary antioxidant; and

(g)0.01 to 2 wt% of at least one secondary antioxidant;

the weight percentages of all components add up to 100 wt.%, and the content of crosslinking promoter is more preferably 1 to 2 wt.%, based on the total weight of the composition.

The foamed articles of the present invention may be made by curing the foamed composition at a temperature in the range of 80 ℃ to 120 ℃, preferably in the range of 95 ℃ to 105 ℃.

In some embodiments of the invention, the foamed article may be prepared by:

a) mixing the components of the foaming composition at a temperature of 15 ℃ to 55 ℃ to form a homogeneous mixture;

b) granulating the homogeneous mixture by extrusion at a temperature of 90 ℃ to 100 ℃ to obtain foamed particles; and

c) forming a foamed article from the foamed particles by injection molding at a temperature of 95 ℃ to 105 ℃.

The foamed article of the present invention may be prepared by heating the foamed article at a temperature of 130 ℃ to 200 ℃. In some embodiments of the invention, the foamed article may be heated for 10 to 120 minutes, preferably 20 to 60 minutes, and most preferably 30 to 40 minutes.

In the present invention, the initial volume expansion ratio (R) of the foamed article can be determined by the following steps:

(a) measuring the volume (Vi) of the foamed article;

(b) obtaining a foamed article by heating the foamed article at a temperature of 130 ℃ to 200 ℃;

(c) cooling the foamed article to room temperature;

(d) measuring the volume (Vf) of the foamed article; and

(e) the initial volume expansion ratio (R) of the foamed product is calculated by the formula R ═ Vf/Vi.

In the present invention, the volume expansion ratio (Rs) of the foamed article after storage can be determined by the following steps:

(a) measuring the volume (Vi) of the foamed article;

(b) storing the foamed article at 40 ℃ and 50% RH for 6 months;

(c) obtaining a foamed article by heating the foamed article after storage at a temperature of 130 ℃ to 200 ℃;

(d) cooling the foamed article to room temperature;

(e) measuring the volume (Vs) of the foamed article; and

(f) the volume expansion ratio (Rs) of the foamed product after storage was calculated by the formula Rs ═ Vs/Vi.

In the present invention, the change in volume expansion ratio (Rc) of the foamed article after storage can be determined by the following steps:

Rc＝(Rs-R)/R；

wherein Rc is the change in volume expansion ratio;

rs-the volumetric expansion of the foamed article after storage; and is

R ═ initial volume expansion of the foamed article.

The initial volume expansion (R) of the foamed article of the present invention is preferably equal to or greater than 2400% after heating at a temperature of 150 ℃.

The initial volume expansion (R) of the foamed article of the present invention is preferably equal to or greater than 750% after heating at a temperature of 140 ℃.

The initial volume expansion (R) of the foamed article of the present invention is preferably equal to or greater than 360% after heating at a temperature of 130 ℃.

The foamed article of the present invention preferably has a volume expansion ratio (Rs) greater than or equal to the initial volume expansion ratio (R) after 6 months of storage at 40 ℃ and 50% RH.

The foamed article of the present invention preferably has a volume expansion ratio change (Rc) of at least 5%, at least 12%, at least 22%, or at least 26% when stored for 6 months at 40 ℃ and 50% RH and then heated at a temperature of 140 ℃.