TW201516080A - Foamable thermoplastic vulcanization body composition and its application - Google Patents

Abstract

A foamable thermoplastic vulcanization body composition includes a crosslinking phase, a base-material phase, and a foaming agent. The crosslinking phase comprises an elastomer, and the base-material phase comprises a thermoplastic. The present invention also provides the manufacturing method of a foamable thermoplastic vulcanization body material, which is to dynamically vulcanize the foamable thermoplastic vulcanization body composition to obtain a foamable thermoplastic vulcanization body material and to foam the foamable thermoplastic vulcanization body composition to obtain the foaming thermoplastic vulcanization body material. The present invention also provides the manufacturing method of a foaming thermoplastic vulcanization body product, which is to treat the aforementioned foaming thermoplastic vulcanization body material by a thermoplastic method; or simultaneously foam and treat by thermoplastic method the aforementioned foamable thermoplastic vulcanization body material to obtain the foaming thermoplastic vulcanization body product. The size of the application hole manufactured by the foamable thermoplastic vulcanization body composition has uniform distribution and low density, and provides the better buffer.

Description

Foamable thermoplastic sulfide composition and application thereof

A foamable thermoplastic sulfide composition and application thereof, in particular to a foamable thermoplastic sulfide composition comprising a foaming agent before dynamic curing, and a use thereof.

Thermoplastic elastomer refers to a mixture of thermoplastics and elastomers, which has elastomeric properties at room temperature, such as high elongation, low permanent set and good Fatigue resistance, etc.; at high temperatures, it has the workability of thermoplastic plastics, such as injection molding, extrusion molding, blow molding, thermoforming (thermoforming) ) or melting, etc., because thermoplastic elastomers have the characteristics of thermoplastics and elastomers, there are many industrial applications, such as the automotive industry and the home appliance industry.

A thermoplastic vulcanizate material is a thermoplastic elastomer which is obtained by dynamically vulcanizing a thermoplastic vulcanization composition comprising a crosslinked phase and a matrix phase comprising an elastomer and a crosslinking agent, the matrix phase comprising a thermoplastic plastic, dynamically vulcanizing the thermoplastic sulfide composition to crosslink the phase and the matrix The mixture is crosslinked and crosslinked to form a crosslinked network structure. The thermoplastic vulcanizate material generally has low permanent strain, good oil resistance, weather resistance and heat resistance, and is therefore widely used in many industries.

In the plastics industry, in addition to reducing the density of plastics and reducing costs, the foaming process can also provide floating, sound insulation, and plastics. Heat insulation or improve its cushioning ability.

The foaming of the existing thermoplastic vulcanized material is carried out after the cross-linking phase and the matrix phase are dynamically vulcanized, and then foamed by a foaming agent to obtain a foamed thermoplastic vulcanized material (foamed thermoplastic vulcanizate material). Since the thermoplastic vulcan material has been dynamically vulcanized, a crosslinked network structure has been formed inside, so that the subsequently added foaming agent does not easily enter the thermoplastic vulcan material, so that the foamed thermoplastic vulcanized material obtained by subsequent foaming is The size and distribution of voids formed are uneven, which also results in the effect of reducing the density of the foamed thermoplastic vulcanic material or the buffering ability; and the use of thermoplastic vulcanized materials The foamed thermoplastic vulcanic material obtained by the foaming process generally has a density of less than 0.5 g/cm ³ .

Another existing foaming process utilizes a physical foaming agent such as carbon dioxide and allows the physical blowing agent to enter through super critical fluid technology. The thermoplastic vulcanized material is foamed in the cross-linked structure, but the equipment required for the supercritical fluid technology is expensive and difficult to control, so that most of them can only be applied to a film product, and the application surface is limited.

Furthermore, the existing foamed thermoplastic vulcanizate material can be treated by a thermoplastic method such as injection molding, hot press molding, extrusion molding or smelting to obtain a foamed thermoplastic vulcanizate article. However, the resulting foamed thermoplastic vulcanizate product has a pore structure which is easily collapsed during the treatment by a thermoplastic process.

Therefore, it is necessary to develop a foamable thermoplastic sulfide composition and a method for producing a foamed thermoplastic vulcanized material and a foamed thermoplastic vulcanized product by using the expandable thermoplastic vulcanized composition, which does not require use. Expensive and difficult to control equipment, and the resulting foamed thermoplastic vulcanizate and foamed thermoplastic vulcanizate have uniform pore size and distribution to provide good density reduction and better cushioning capacity.

In order to overcome the foregoing objects, the present invention provides a foamable thermoplastic vulcanizate composition comprising: a crosslinked phase, a matrix phase and a foaming agent. The crosslinked phase comprises an elastomer comprising a thermoplastic.

The present invention also provides a method for producing a foamed thermoplastic vulcan material, comprising: preparing the foregoing foamable thermoplastic vulcanization composition; dynamically vulcanizing and foaming the foamable thermoplastic vulcanization composition to form the foam Thermoplastic sulfide material.

Since the foaming agent is initially included in the foamable thermoplastic sulfide composition, the foaming agent is sufficiently mixed with the matrix phase during the dynamic vulcanization to cause foaming. The pores formed after the uniform size and distribution are also effective in reducing the density of the obtained foamed thermoplastic vulcanizate material and providing better buffering capacity.

Preferably, the foamable thermoplastic vulcanization composition is dynamically vulcanized to form a foamable thermoplastic vulcanizate material, and then the foamable thermoplastic vulcan material is foamed to form the hair. Bubble thermoplastic vulcan material.

Preferably, the foamable thermoplastic sulfide composition is dynamically vulcanized and foamed simultaneously to form the foamed thermoplastic sulfide material.

Preferably, in the step of dynamically vulcanizing and foaming the foamable thermoplastic sulfide composition, the crosslinked phase of the foamable thermoplastic sulfide composition further comprises a crosslinking agent, and the vulcanization is dynamically vulcanized. The thermoplastic vulcanization composition is performed by heating or radition, and the crosslinking agent may be an alkyl peroxide compound or a dialkyl peroxide compound. Peroxide ester compounds, peroxyketal compounds, acetyl peroxide compounds or peroxide dicarbonate compounds; Preferably, the peroxy ketal compound is 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxydecane (3,6,9-triethyl -3,6,9-trimethyl-1,4,7-triperoxonane), 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane (1,1-bis(t- Butylperoxy)-3,3,5-trimethylcyclohexane, Luperox 231), 1,1-di(tert-butylperoxycyclohexane) or 2-2- (2,2-di(tert-butylperoxy)butane); preferably, the crosslinking agent is 1,1-di-tert-butylperoxy-3,3,5-three Methylcyclohexane.

Preferably, in the step of dynamically vulcanizing and foaming the foamable thermoplastic sulfide composition, the crosslinked phase of the foamable thermoplastic sulfide composition further comprises a co-agent, the auxiliary The crosslinking agent comprises at least one vinyl group; more preferably, the co-crosslinking agent is triallyl cyanurate, triallyl isocyanurate , triallyl phosphate or divinyl benzene; preferably, the co-crosslinking agent is triallyl cyanurate.

Preferably, the dynamic vulcanization of the foamable thermoplastic vulcanization composition is carried out by heating at a temperature between 160 and 190 degrees Celsius.

Preferably, in the step of dynamically vulcanizing and foaming the foamable thermoplastic sulfide composition, the foaming agent of the foamable thermoplastic sulfide composition is a physical foaming agent, and the foaming foaming The thermoplastic vulcanization composition is carried out by heating; more preferably, the physical blowing agent is water, hydrocarbon or expandable microspheres.

Preferably, in the step of dynamically vulcanizing and foaming the foamable thermoplastic sulfide composition, the foaming agent of the foamable thermoplastic sulfide composition is a chemical foaming agent, and The foamable thermoplastic sulfide composition is carried out by heating; more preferably, the chemical blowing agent is azocompounds or azide compounds; preferably, the azo compound is azo Azobisisobutyronitrile, azodicarbonamide, azocyclohexylnitrile, barium azodicarboxylate or azodiaminobenzene.

Preferably, foaming the foamable thermoplastic sulfide composition is carried out by heating at a temperature between 190 and 230 degrees Celsius.

Preferably, in the step of dynamically vulcanizing and foaming the foamable thermoplastic vulcanization composition, the elastomer of the foamable thermoplastic vulcanization composition is natural rubber or butyl rubber (isobutyleneisoprene butyl rubber). ), polybutadiene rubber, acrylate rubber, polychloroprenerubber, acrylonitrile butadiene rubber, styrene butadiene rubber or ethylene copolymerization More preferably, the elastomer is an ethylene copolymer, such as an ethylene-olefin copolymer, an ethylene propylene diene monomer rubber, an ethylene vinyl acetate. (ethylene vinyl acetate) or ethylene glycidyl methacrylate.

Preferably, in the step of dynamically vulcanizing and foaming the foamable thermoplastic vulcanization composition, the thermoplastic of the foamable thermoplastic vulcanization composition is a homopolymer or copolymerization of propylene. Copolymer, ethylene homopolymer or copolymer, homopolymer or copolymer of butadiene, homopolymer or copolymer of isoprene, benzene A homopolymer or copolymer of styrene, a homopolymer or copolymer of acrylonitrile, poly(methyl methacrylate), polyamide, polylactic acid (polylactic acid), polycarbonate (carbonate) or a mixture thereof.

Preferably, in the step of dynamically vulcanizing and foaming the foamable thermoplastic sulfide composition, the total weight of the foamable thermoplastic sulfide composition is 100%, and the weight percentage of the crosslinked phase (weight percentage) , Wt%) is 55 to 90%.

Preferably, in the step of dynamically vulcanizing and foaming the foamable thermoplastic sulfide composition, the total weight of the foamable thermoplastic sulfide composition is 100%, and the weight percentage of the matrix phase is 10 to 45. %.

Preferably, in the step of dynamically vulcanizing and foaming the foamable thermoplastic sulfide composition, the total weight of the foamable thermoplastic sulfide composition is 100%, and the foamable thermoplastic sulfide is composed of a composition The weight percentage of the phase is 55 to 90%.

Preferably, the foamed thermoplastic vulcanizate material has a density greater than 0.05 g/cm 3 ; more preferably, the foamed thermoplastic vulcan material material has a density greater than 0.10 g/cm 3 ; That is, the density of the foamed thermoplastic vulcanic material produced is greater than 0.20 g/cm 3 . In another embodiment of the present invention, in the step of dynamically vulcanizing and foaming the foamable thermoplastic sulfide composition, the crosslinked phase of the foamable thermoplastic sulfide composition further comprises a crosslinking agent and a touch Catalyst, the cross-linking agent is bis(dimethylsilyl)benzene, bis(dimethylsilyl)kanes, methyl- Hydroxyalkyl alkyl methyl polysiloxanes, methylhydrogen dimethyl-siloxane copolymer or methylhydrogen dimethyl-siloxane copolymer Polysiloxanes; the catalyst is a catalyst comprising a Group VIII transition metal, and the catalyst comprising a Group VIII transition metal is dichloro-bis(triphenylphosphine)platinum (II) (dichloro-bis) (triphenylphosphine) platinum (II)), cis-dichloro-bis(acetonitrile) platinum (II), dicarbonyldichloroplatinum (II) , platinum chloride or platinum oxide.

In still another embodiment of the present invention, in the step of dynamically vulcanizing and foaming the foamable thermoplastic sulfide composition, the crosslinked phase of the foamable thermoplastic sulfide composition further comprises a crosslinking agent. The crosslinking agent is a resole which is obtained by polycondensation of a substituted or unsubstituted phenol and aldehyde in an alkaline environment, and has at least one active hydroxyl group. A methyl group (methylolgroup).

The present invention further provides a method of producing a foamed thermoplastic vulcanizate comprising: subjecting the foamed thermoplastic vulcanic material obtained as described above to a thermoplastic process to form the expanded thermoplastic vulcanizate product.

The present invention further provides a method for producing a foamed thermoplastic vulcanizate comprising: preparing a foamable thermoplastic sulfide composition; dynamically vulcanizing the foamable thermoplastic sulfide composition to form a foamable thermoplastic sulfide material; And simultaneously foaming and thermoplastically treating the foamable thermoplastic vulcan material to form a foamed thermoplastic vulcanizate; wherein the foamable thermoplastic vulcanizate comprises a crosslinked phase, a matrix phase and A blowing agent comprising an elastomer and a crosslinking agent, the matrix phase comprising a thermoplastic.

Preferably, the foamed thermoplastic vulcanic material is treated by a thermoplastic process by injection molding, hot press forming, extrusion molding or smelting.

Preferably, the foamed thermoplastic vulcanizate product has a density greater than 0.05 g/cm 3 ; more preferably, the foamed thermoplastic vulcanizate product has a density greater than 0.10 g/cm 3 ; That is, the density of the foamed thermoplastic vulcanizate produced is greater than 0.20 g/cm 3 . Based on the above, the method for producing a foamed thermoplastic vulcan material according to the present invention can be easily processed to obtain a foamed thermoplastic vulcanized material having a uniform pore size and a uniform distribution, and a foamed thermoplastic vulcanizate product, thereby providing a good density reduction. Materials with good results and better cushioning capacity are available for various industrial applications.

The present invention provides a foamable thermoplastic vulcanization composition comprising: a crosslinked phase, a matrix phase and a blowing agent, the crosslinked phase comprising an elastomer comprising a thermoplastic.

The present invention further provides a method for producing a foamed thermoplastic vulcan material, which is provided with the above-mentioned foamable thermoplastic vulcanization composition; dynamically vulcanizes and foams the foamable thermoplastic vulcanized composition to form the foamed thermoplastic vulcanizate. Body material.

The elastomer is defined by the American Society for Testing and Materials, and refers to a marco-molecule material that can be restored to its original state at room temperature after the external force that deforms it is removed. The appearance and size of the person. Non-limiting examples of the elastomer are natural rubber, butyl rubber, butadiene rubber, acrylic rubber, neoprene rubber, acrylonitrile butadiene rubber, styrene butadiene rubber, halogenated rubber, epichlorohydrin. (epichlorohydrin) or ethylene copolymer.

A non-limiting example of a halogenated rubber is bromo isobutylene isoprene rubber or chloro isobutylene isoprene rubber.

Non-limiting examples of ethylene copolymers are ethylene-olefin copolymers, ethylene propylene diene rubber, ethylene vinyl acetate or ethylene epoxy propyl methacrylate.

In the ethylene-olefin copolymer, an olefin is generally selected from α-olefins, and non-limiting examples of α-olefins are 1-butene (1-butylene) and 1-hexene (1-hexene). , 4-methyl-1-pentene, 1-octene or 1-decene.

A non-limiting example of commercialization of ethylene-olefin copolymers is the EngageTM series (Dow Chemical).

The thermoplastic is conventionally defined to soften when applied to heat and to restore its original properties upon cooling, non-limiting examples of which are homopolymers or copolymers of propylene, homopolymers or copolymers of ethylene, and Homopolymer or copolymer of dienes, homopolymer or copolymer of isoprene, homopolymer or copolymer of styrene, homopolymer or copolymer of acrylonitrile, polymethacrylic acid Methyl ester, polyamine, polycarbonate, polyvinyl chloride, polylactic acid or a mixture thereof.

A non-limiting example of commercialization of propylene homopolymers or copolymers is the Globalene series (Li Changrong Chemical Industry Co., Ltd.).

A non-limiting example of commercialization of a homopolymer or copolymer of styrene is the Taipol® series (Taiwan Synthetic Rubber Co., Ltd.).

Dynamic vulcanization refers to mixing and cross-linking the cross-linked phase with the matrix, but is not limited to, peroxide curatives system, silicon-containing curatives system or phenolic system. A phenolic resin curatives system.

Dynamic vulcanization is, for example, but not limited to, roll-compounder, Banbury mixers, Brabender mixers, continuous mixers, mixed extrusion Mixing extruders, such as single screw extruder/twin screw extruder.

The cross-linking through the peroxide curing system is carried out by adding a crosslinking agent and a co-crosslinking agent to the cross-linking phase, and performing heating or illuminating.

Non-limiting examples of crosslinking agents in peroxide curing systems are alkyl peroxide compounds, dialkyl peroxide compounds, peroxy acid ester compounds, peroxy ketals, sulfhydryl groups. An oxide compound or a peroxydicarbonate compound.

Non-limiting examples of alkyl peroxide compounds are tert-butyl hydroperoxide, tert-amyl hydroperoxide or 2,5-dimethyl-2,5 (2,5-dimethylhexane 2,5-dihydroperoxide).

Non-limiting examples of dialkyl peroxide compounds are di-tert-butyl peroxide, di-tert-amyl hydroperoxide, 2,5-di Methyl-2,5-bis(tert-butylperoxy-2,5-dimethylhexane) or 2,5-dimethyl-2,5-bis (tert-butyl) Base oxidized) 2,5-dimethyl-2,5-di(tertiary-butylperoxy)-hexyne-3).

Non-limiting examples of peroxyacid ester compounds are tert-butyl peroxybenzoate, tert-amyl peroxybenzoate, tert-butyl peroxyacetate. ), tert-Butyl monoperoxymaleate, tert-butyl peroxypivalate, tert-butyl peroxyneodecanoate, new peroxidation Tert-Amyl peroxyneodecanoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyisobutyrate, Oxidized tert-butyl peroxyneoheptanoate, tert-butyl peroxy-3,5,5-trimethylhexanoate, 2-B-peroxide Tert-butylperoxy 2-ethylhexyl carbonate, tert-Amylperoxy 2-ethylhexyl carbonate or 2,5-dimethyl-2,5- Bis(2-ethylhexanoylperoxy)hexane (2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane).

A non-limiting example of a peroxy ketal compound is 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxydecane (3,6,9-Triethyl) -3,6,9-trimethyl-1,4,7-triperoxonane), 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane (1,1-bis(tert- Butylperoxy)-3,3,5-trimethylcyclohexane), 1,1-bis(tert-butylperoxycyclohexane) or 2,2-di(tert-butylperoxide) ) Butane (2,2-di(tert-butylperoxy)butane).

A non-limiting example of commercialization of peroxy ketals is the Luperox® series (Arkema Ltd.).

Non-limiting examples of sulfhydryl peroxide compounds are benzoyl peroxide, bis(3,5,5-trimethylhexanyl peroxide) (peroxide, bis(3,5,5-). Trimethyl-1-oxohexyl)) or dilauroyl peroxide.

Non-limiting examples of peroxydicarbonate compounds are peroxydicarbonic acid (di(2-ethylhexyl)ester), bis(4-tert-butylcyclopentoxide) peroxydicarbonate (bis(4-tert-butylcyclohexyl) peroxydicarbonate), dimyristyl peroxydicarbonate or dicetelyl peroxydicarbonate.

The co-crosslinking agent in the peroxide curing system comprises at least one vinyl group, non-limiting examples of which are triallyl cyanurate, triallyl cyanurate, triallyl phosphate or two Vinyl benzene.

The crosslinking is carried out by adding a crosslinking agent and a catalyst through the ruthenium-containing curing system.

The crosslinking agent in the cerium-containing curing system comprises at least two SiH-based compounds of silicon hydride, and the carbon-carbon double bond of the elastomer in the crosslinked phase and the thermoplastic in the matrix phase The reaction is carried out in the presence of the catalyst, and non-limiting examples thereof are bis(dimethylformamidine)benzene, bis(dimethylformamidine)alkane, methyl-hydrogen-dimethyloxane copolymer, Methyl-hydrogen-polyoxyalkylene or a mixture thereof.

A non-limiting example of a catalyst in a cerium-containing curing system is a catalyst comprising a Group VIII transition metal, and non-limiting examples of Group VIII transition metals are palladium, rhodium, and platinum. And a complex of these metals; a non-limiting example of a platinum complex is dichloro-bis(triphenylphosphine)platinum (II), cis-dichloro-bisacetonitrile platinum (II), dicarbonyl II Chloroplatinum, platinum chloride or platinum oxide.

The phenolic resin curing system is crosslinked to the crosslinked phase by adding a crosslinking agent, which is a resol phenolic resin, which is substituted or unsubstituted phenol and formaldehyde in an alkaline environment. It is obtained by polycondensation and has at least one reactive methylol group.

A non-limiting example of commercialization of resoles is the Cellbond® or Durite® series (Metute Chemicals).

The foaming agent is a physical foaming agent or a chemical foaming agent, and the foaming of the foamable thermoplastic sulfide composition is carried out by heating.

Non-limiting examples of physical blowing agents are water, hydrocarbons or expandable microspheres which vaporize and diffuse when the temperature is above the boiling point of the physical blowing agent.

Non-limiting examples of hydrocarbons are propane, butane, pentane, fluorocarbons, hydrofluorocarbons, chlorofluorocarbons or nitrogen. (nitrogen).

The expandable microspheres are microscopic shperes composed of a thermoplastic shell coated with a liquid electrolyte of a low boiling point liquid. When the expandable microspheres are heated until the thermoplastic shell softens, the pressure due to vaporization of the hydrocarbon will increase the volume of the expandable microspheres. A non-limiting example of its commercialization is the Expancel® series (Akzo Nobel GmbH).

Non-limiting examples of chemical blowing agents are sodium carbonate, sodium hydrogen carbonate, ammonium carbonate, ammonium hydrogen carbonate, ammonium nitrite. , nitrous compounds, azo compounds, azide compounds, sulfonylhydrazide compounds, when the energy provided by the temperature is higher than the bond energy in the chemical blowing agent molecule, chemical foaming The agent breaks the bond and forms a gas phase molecule.

A non-limiting example of a compound of nitrous acid is N,N'-dinitrosopentamethylenetetramine or N,N'-dimethyl-N,N'-di Nitro-p-xylamine (N, N'-dimethyl-N, N'-dinitrosoterephthalamide).

Non-limiting examples of azo compounds are azobisisobutyronitrile, azobisformamide, azocyclohexylnitrite, guanidine azodicarboxylate or azobenzenediamine.

Non-limiting examples of azide compounds are 4,4'-diphenyldisulfonylazide, p-toluenesulfonylazide or azide. Calcium azide.

Non-limiting examples of sulfonium compounds are benzenesulfonylhydrazide, p,p'-oxybis(benzenesulfonylhydrazide) or diphenylsulfone-3,3 '-Diphenylsulfone-3, 3'-disulfonylhydrazide.

The foamable thermoplastic sulfide composition may further comprise an additive, which is an antioxidant, a pigment, a wax, an antisticking agent, an antistatic agent. , UV stabilizers, fire retardants or other processing aids well known in rubber synthesis.

Non-limiting examples of antioxidants are hindered phenols, organophosphites, thioesters, or mixtures thereof.

Non-limiting examples of hindered phenols are 2,6-di-tert-butyl-4-methylphenol, tetrakis(3-(3',5')-di-tertiary Pentaerythritoltetrakis (3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) or 3,5-di-tert-butyl-4-hydroxyl Octadecyl-3, 5-di-tert-butyl-4-hydroxy-hydrocinnamate.

A non-limiting example of commercialization of hindered phenols is the Igranox® series (Ciba Specialty).

Non-limiting examples of organophosphite compounds are tris(nonylphenyl)phosphite, isooctyl diphenylphosphite, triphenyl phosphite (triphenyl) Phosphine) or tris(2,4-di-tert-butylphenyl)phosphite.

A non-limiting example of a commercialization of organic phosphites is the Irgafos® series (Ciba Specialty).

A non-limiting example of a thioester compound is disearyl 3,3'-thiodipropionate.

The foamed thermoplastic vulcan material obtained can be formed into a foamed thermoplastic vulcanizate by a thermoplastic process.

In a preferred embodiment, the thermoplastic process is, for example, but not limited to, injection molding, extrusion molding, or hot press molding or smelting, which are conventional techniques and will not be further described.

Hereinafter, an embodiment of the method for producing the foamed thermoplastic vulcan material will be described by the following specific examples, and those skilled in the art can easily understand the advantages and effects of the present invention through the contents of the specification, and Various modifications and changes are made in the spirit of the invention to practice or apply the invention. Example 1

As shown in Figure 1, a foamable thermoplastic vulcanizate composition is first placed in a Brabender mixer at an initial temperature of 130 degrees and a temperature of 170 to 180 degrees Celsius (revolution per minute, rpm). The foaming thermoplastic vulcanization composition is dynamically vulcanized by sub-mixing heating for 7 to 10 minutes to form a foamable thermoplastic vulcan material, which is then foamed in a hot press at a temperature of 230 degrees Celsius in a mold having a volume of 60 cubic centimeters. The foamable thermoplastic vulcan material can be obtained by foaming a thermoplastic vulcan material for 5 to 6 minutes.

Wherein, the foamable thermoplastic sulfide composition comprises a crosslinked phase, a matrix phase, a foaming agent and an additive, the crosslinked phase comprising an elastomer, a crosslinking agent and a co-crosslinking agent, the elasticity The body is EngageTM 8200, the crosslinking agent is Luperox® 231, the co-crosslinking agent is triallyl cyanurate; the matrix phase comprises a thermoplastic plastic, which is Globalene6733, Taipol® 6150 and polylactic acid. a mixture; the blowing agent is azobisformamide; the additive is Igranox® 1010.

The total weight of the foamable thermoplastic sulfide composition is 100%, and the crosslinked phase: matrix phase: foaming agent: weight percent of the additive is 66.4: 33.0: 0.5: 0.1; elastomer: crosslinker: assist The weight percentage of the crosslinking agent is 64.4:1.5:0.5; Globalene6733: Taipol® 6150: The weight percentage of polylactic acid is 10.2:7.6:15.2. Example 2

In this embodiment, a foamed thermoplastic vulcan material is prepared substantially by the method as in the foregoing Example 1, except that the ratio of the expandable thermoplastic vulcanizate composition in this embodiment is different from that in Embodiment 1, and the details thereof As follows, the total weight of the foamable thermoplastic sulfide composition is 100%, and the crosslinked phase: matrix phase: foaming agent: weight percent of the additive is 65.7: 32.7: 1.5: 0.1; elastomer: crosslinking agent The weight percentage of the co-crosslinking agent is 63.7:1.5:0.5; Globalene 6733: Taipol® 6150: the weight percentage of polylactic acid is 10.2:7.5:15.0. Example 3

In this embodiment, a foamed thermoplastic vulcan material is prepared substantially by the method as in the foregoing Example 1, except that the ratio of the expandable thermoplastic vulcanizate composition in this embodiment is different from that in Embodiment 1, and the details thereof As follows, the total weight of the foamable thermoplastic sulfide composition is 100%, and the crosslinked phase: matrix phase: foaming agent: weight percent of the additive is 64.7: 32.2: 3.0: 0.1; elastomer: crosslinking agent The weight percentage of the co-crosslinking agent is 62.7:1.5:0.5; Globalene 6733: Taipol® 6150: The percentage by weight of polylactic acid is 10.0:7.4:14.8. Example 4

As shown in FIG. 2, the foamable thermoplastic sulfide composition in this embodiment is only in a ratio different from that of Example 1, and the foamable thermoplastic sulfide composition is placed in a Brabender mixer at an initial temperature. 130 degrees, an end temperature of 170 to 180 degrees Celsius is mixed and heated at a speed of 100 rpm for 7 to 10 minutes to dynamically vulcanize the foamable thermoplastic sulfide composition to form the foamable thermoplastic sulfide material, and the expandable thermoplastic vulcanization is performed. The body material was foamed by a single screw extruder (length to diameter ratio of 25, screw diameter of 35 mm, die width of 15 mm, die opening size of 1.5 mm) at a rotation speed of 30 rpm, a temperature of 230 ° C and extruded to form a foamed thermoplastic vulcanizate. product. Wherein, the total weight of the foamable thermoplastic sulfide composition is 100%, and the crosslinked phase: matrix phase: foaming agent: weight percentage of the additive is 66.4: 33.0: 0.5: 0.1; elastomer: crosslinking agent The weight percentage of the co-crosslinking agent is 64.4:1.5:0.5; Globalene6733: Taipol® 6150: The weight percentage of polylactic acid is 10.2:7.6:15.2. Example 5

As shown in FIG. 3, this embodiment prepares a foamed thermoplastic vulcan material by the method as in the foregoing Example 1, and then the obtained foamed thermoplastic vulcan material is placed in a Brabender mixer at a temperature. The foamed thermoplastic vulcanizate product is obtained after heating at 170 to 180 degrees Celsius for 2 minutes. Example 6

As shown in FIG. 4, the foamable thermoplastic sulfide composition in this example was the same as in Example 2, and the foamable thermoplastic sulfide composition was placed in a Brabender mixer at an initial temperature of 130 degrees. The end temperature is 230 degrees Celsius and mixed and heated at a rotation speed of 100 rpm for 7 to 10 minutes while dynamically vulcanizing and foaming the foamable thermoplastic sulfide composition to form the foamable thermoplastic sulfide material. Comparative Example 1

As shown in FIG. 5, in this comparative example, a thermoplastic vulcan material is selected, which is Elastoplas® KP-501-N55 (National Chemical Co., Ltd.), and the thermoplastic vulcanic material is placed in Bula. The foamable thermoplastic vulcan material is obtained by adding a blowing agent in a Bayer mixer and heating and mixing at a temperature of 170 to 180 degrees Celsius for 2 minutes, and then the foamable thermoplastic vulcanized material is in a volume of 60 cubic centimeters. The mold was foamed in a hot press at a temperature of 230 ° C for 5 to 6 minutes to form the foamed thermoplastic vulcan material.

Wherein, the foaming agent is azobisformamide, and the total weight of the thermoplastic sulfide material and the foaming agent is 100%, and the weight percentage of the thermoplastic sulfide material: foaming agent is 98.5:1.5. Comparative Example 2

This comparative example was prepared by the method of the above Comparative Example 1, except that the total weight of the thermoplastic sulfide material and the foaming agent was 100% in this comparative example, and the thermoplastic vulcanic material was used. The weight percentage of the blowing agent is, for example, 98.0:2.0. Comparative Example 3

This comparative example was substantially prepared by foaming a thermoplastic vulcan material as in the foregoing Example 1, except that the foamable thermoplastic vulcanizate composition of this comparative example was mixed in a Brabender mixer. And the foaming agent is not included before heating, and the detailed procedure is as follows. The foamable thermoplastic sulfide composition not containing the foaming agent is placed in a Brabender mixer, and the initial temperature is set to 130 degrees, and the temperature is ended at 170 degrees Celsius. Dynamically vulcanizing the foamable thermoplastic vulcanization composition containing no blowing agent to a temperature of 100 rpm at 100 rpm for 7 to 10 minutes to form the thermoplastic vulcanized material, followed by adding a blowing agent and then at a temperature of 170 ° C The foamable thermoplastic vulcan material is obtained by heating and mixing for 2 minutes to 180 degrees, and the foamable thermoplastic vulcan material is heated in a hot press at a temperature of 230 degrees Celsius for 5 to 6 minutes in a mold having a volume of 60 cubic centimeters. The foamed thermoplastic vulcan material is foamed.

Wherein, the foaming agent is azobisformamide, and the total weight of the foamable thermoplastic sulfide composition not containing the foaming agent and the foaming agent is 100%, and the crosslinking phase: matrix phase: Foaming agent: The weight percentage of the additive is 66.1:32.8:1.0:0.1; Elastomer: Crosslinking agent: The weight percentage of the crosslinking agent is 64.1:1.5:0.5; Globalene6733: Taipol® 6150: The weight of polylactic acid The percentage example is 10.1:7.6:15.1. Comparative Example 4

This comparative example is substantially prepared by the method of the above Comparative Example 3, except that the ratio of the foamable thermoplastic sulfide composition not containing the foaming agent to the foaming agent is different. The details are as follows, the total weight of the foamable thermoplastic sulfide composition not containing the foaming agent and the foaming agent is 100%, and the crosslinked phase: matrix phase: foaming agent: weight percentage of the additive 65.9:32.7:1.3:0.1; elastomer: crosslinker: weight percentage of co-crosslinking agent is 63.9:1.5:0.5; Globalene 6733: Taipol® 6150: weight percentage of polylactic acid is 10.1:7.5:15.1 . Comparative Example 5

As shown in Fig. 6, this comparative example was prepared by foaming a thermoplastic vulcan material by the method as in the above Comparative Example 1, and then the obtained foamed thermoplastic vulcan material was placed in a Brabender mixer at a temperature. The foamed thermoplastic vulcanizate product can be obtained by heating at 170 to 180 degrees Celsius for 2 minutes. Test case

The density before foaming and the density after foaming of each of the examples and the comparative examples were obtained in accordance with the measurement method in the ASTM D792 specification, and the results are shown in Table 1.

Comparing Examples 1 to 3 with Comparative Examples 1 to 2, in Examples 1 to 3, since the blowing agent was added to the foamable thermoplastic sulfide composition immediately before the dynamic vulcanization, in the course of dynamic vulcanization, The foaming agent is thoroughly mixed with the crosslinking phase and the matrix phase, so that the pores and the distribution of the pores formed by the foaming thermoplastic sulfide material obtained by the subsequent foaming are uniform, and the density after foaming is less than 0.6 g/cm 3 . And Comparative Examples 1 to 2, the thermoplastic vulcan material (Elastoplas® KP-501-N55) is mixed with the foaming agent, and since the thermoplastic vulcan material has been dynamically vulcanized, a crosslinked network structure has been formed inside. Therefore, the foaming agent added later is not easy to enter the thermoplastic vulcanized material, so that the subsequent foaming is almost only foamed in the matrix phase, so that the pore size and distribution of the obtained foamed thermoplastic vulcan material are not uniform. The density after foaming is greater than 0.7 g/cm 3 .

Comparative Examples 1 to 3 and Comparative Examples 3 to 4, although the foamable thermoplastic sulfide composition was prepared using the same foamable thermoplastic sulfide composition as in the examples, Comparative Examples 3 and 4 were not used before dynamic vulcanization. The foaming agent is added to the foamable thermoplastic vulcanization composition, so that the foaming agent added later does not easily enter the thermoplastic vulcanized material, so that the subsequent foaming is almost only foamed in the matrix phase, so the resulting foamed thermoplastic The size and distribution of the pores formed by the sulfide material are not uniform.

In Example 4, the foamable thermoplastic sulfide composition is added to the blowing agent prior to dynamic vulcanization, so that during the dynamic vulcanization, the blowing agent is thoroughly mixed with the crosslinking phase and the matrix phase. Even if the subsequent foaming is accompanied by a thermoplastic method such as extrusion molding, the size and distribution of the pores of the formed foamed thermoplastic vulcanizate product are uniform.

Comparing Example 5 and Comparative Example 5, even if the foamed thermoplastic vulcanic material was further heated and smelted in Example 5, the size and distribution of the voids of the formed foamed thermoplastic vulcanizate product were uniform; In the fifth embodiment, the foamed thermoplastic vulcanized material is further heated and smelted, and the formed foamed thermoplastic vulcanizate product has no pores, and the density after molding is greater than 0.9 g/cm 3 , thereby knowing the foamed thermoplastic vulcanizate. The material can be further processed in a thermoplastic process without affecting the size and distribution of the voids of the foamed thermoplastic vulcanizate product formed.

In Example 6, the foamable thermoplastic sulfide composition is added to the blowing agent prior to dynamic vulcanization, so that during the dynamic vulcanization and foaming process, the blowing agent is allowed to interact with the crosslinking phase and the matrix phase. The mixture is sufficiently mixed to make the pores and the distribution of the foamed thermoplastic vulcanized material obtained by subsequent foaming uniform, and the density after foaming is less than 0.4 g/cm 3 .

The above-mentioned embodiments are merely examples for convenience of description, and the scope of the claims is intended to be limited to the above embodiments.

[00100] None

FIG. 1 is a flow chart of a preferred embodiment of the present invention. 2 is a flow chart of another preferred embodiment of the present invention. FIG. 3 is a flow chart of still another preferred embodiment of the present invention. 4 is a flow chart of still another preferred embodiment of the present invention. Figure 5 is a flow chart showing one embodiment of the prior art foaming process. Figure 6 is a flow chart showing another embodiment of the prior art foaming process.

Claims (35)

A foamable thermoplastic vulcanizate composition comprising: a crosslinked phase, a matrix phase and a foaming agent, the crosslinked phase comprising An elastomer, the matrix phase comprising a thermoplastic. A method for producing a foamed thermoplastic vulcanizate material, comprising: a foamable thermoplastic vulcanization composition as claimed in claim 1; dynamically vulcanizing and foaming The thermoplastic vulcanizable composition is foamable to form the foamed thermoplastic vulcan material. The method for producing a foamed thermoplastic vulcanizate according to claim 2, wherein the step of dynamically vulcanizing and foaming the foamable thermoplastic vulcanizate comprises: dynamically vulcanizing the foamable thermoplastic vulcanization composition to form a A foamable thermoplastic vulcanizate material; the foamable thermoplastic vulcan material is then foamed to form the foamed thermoplastic vulcan material. The method for producing a foamed thermoplastic vulcanizate according to claim 2, wherein the step of dynamically vulcanizing and foaming the foamable thermoplastic vulcanizate simultaneously dynamic vulcanization and foaming of the foamable thermoplastic vulcanization composition To form the foamed thermoplastic sulfide material. The method for producing a foamed thermoplastic vulcan material according to any one of claims 2 to 4, wherein in the step of dynamically vulcanizing and foaming the foamable thermoplastic vulcan composition, the foamable thermoplastic vulcan composition The cross-linking phase further comprises a crosslinking agent, and the vulcanized thermoplastic vulcanizable body composition is dynamically vulcanized by heating or radition, and the cross-linking agent can be an alkyl peroxide. (alkyl peroxide compounds), dialkyl peroxide compounds, peroxide ester compounds, peroxyketal compounds, thiol peroxides A acetyl peroxide compound or a peroxide dicarbonate compound. According to the method for producing a foamed thermoplastic vulcanizate according to claim 5, the vulcanizable thermoplastic vulcanizate is dynamically vulcanized at a temperature of from 160 to 190 ° C. The method for producing a foamed thermoplastic vulcanizate according to claim 5, wherein in the step of dynamically vulcanizing and foaming the foamable thermoplastic vulcanizate, the crosslinked phase of the expandable thermoplastic vulcanizate composition is further A co-crosslinking agent is included, and the co-crosslinking agent comprises at least one vinyl group. The method for producing a foamed thermoplastic vulcanizate according to claim 5, wherein in the step of dynamically vulcanizing and foaming the foamable thermoplastic vulcanizate, the crosslinked phase of the expandable thermoplastic vulcanizate composition is further A co-crosslinking agent is included, and the co-crosslinking agent is triallyl cyanurate, triallyl isocyanurate, triallyl phosphate or diethylene Divinyl benzene. The method for producing a foamed thermoplastic sulfide material according to claim 5, wherein in the step of dynamically vulcanizing and foaming the foamable thermoplastic sulfide composition, the crosslinked phase of the foamable thermoplastic sulfide composition The crosslinking agent is a peroxy ketal compound, and the peroxy ketal compound is 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxydecane ( 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane), 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane (1 , 1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, Luperox 231), 1,1-di(tert-butylperoxycyclohexane) Or 2-2-di(tert-butylperoxybutane). The method for producing a foamed thermoplastic sulfide material according to claim 5, wherein in the step of dynamically vulcanizing and foaming the foamable thermoplastic sulfide composition, the crosslinked phase of the foamable thermoplastic sulfide composition The crosslinking agent is 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane. The method for producing a foamed thermoplastic vulcan material according to any one of claims 2 to 4, wherein in the step of dynamically vulcanizing and foaming the foamable thermoplastic vulcan composition, the foamable thermoplastic vulcan composition The cross-linking phase further comprises a cross-linking agent and a catalyst, the cross-linking agent being bis(dimethylsilyl)benzene, bis(dimethylformamido) Alkene (bis(dimethylsilyl)alkanes), methylhydrogen alkyl methyl polysiloxanes, methylhydrogen dimethyl-siloxane copolymer Or methyl-hydrogen-polyoxymethane; the catalyst is a catalyst comprising a Group VIII transition metal, and the catalyst comprising a Group VIII transition metal is dichloro-bis ( Dichloro-bis(triphenylphosphine) platinum (II), cis-dichloro-bis(acetonitrile) platinum (II), Dicarbonyldichloroplatinum (II), platinum chloride or oxidation (Platinumoxide). The method for producing a foamed thermoplastic vulcan material according to any one of claims 2 to 4, wherein in the step of dynamically vulcanizing and foaming the foamable thermoplastic vulcan composition, the foamable thermoplastic vulcan composition The cross-linking phase further comprises a cross-linking agent, which is a resole, which is obtained by polycondensation of a substituted or unsubstituted phenol and aldehyde in an alkaline environment. (polycondensation), and has at least one active methylol group. The method for producing a foamed thermoplastic vulcan material according to any one of claims 2 to 4, wherein in the step of dynamically vulcanizing and foaming the foamable thermoplastic vulcan composition, the foamable thermoplastic vulcan composition The foaming agent is a physical foaming agent, and foaming the foamable thermoplastic sulfide composition is carried out by heating. The method for producing a foamed thermoplastic vulcan material according to claim 13, wherein in the step of dynamically vulcanizing and foaming the foamable thermoplastic vulcan composition, physical foaming of the expandable thermoplastic vulcan composition The agent is water, hydrocarbon or expandable microspheres. The method for producing a foamed thermoplastic vulcan material according to any one of claims 2 to 4, wherein in the step of dynamically vulcanizing and foaming the foamable thermoplastic vulcan composition, the foamable thermoplastic vulcan composition The foaming agent is a chemical foaming agent, and foaming the foamable thermoplastic sulfide composition is carried out by heating. According to the method for producing a foamed thermoplastic vulcan material according to claim 15, the foamable thermoplastic vulcanization composition is foamed at a temperature of from 190 to 230 ° C. The method for producing a foamed thermoplastic vulcan material according to claim 15, wherein in the step of dynamically vulcanizing and foaming the foamable thermoplastic vulcan composition, chemical foaming of the expandable thermoplastic vulcan composition The agents are azocompounds or azide compounds. The method for producing a foamed thermoplastic vulcan material according to any one of claims 2 to 4, wherein in the step of dynamically vulcanizing and foaming the foamable thermoplastic vulcan composition, the foamable thermoplastic vulcan composition The foaming agent is a chemical foaming agent, and foaming the foamable thermoplastic sulfide composition is carried out by heating, the chemical foaming agent is an azo compound, and the azo compound is azobisisobutyronitrile. (azobisisobutyronitrile), azodicarbonamide, azocyclohexylnitrile, barium azodicarboxylate or azodiaminobenzene. The method for producing a foamed thermoplastic vulcan material according to any one of claims 2 to 4, wherein in the step of dynamically vulcanizing and foaming the foamable thermoplastic vulcan composition, the foamable thermoplastic vulcan composition The elastomer is natural rubber, isobutylene isoprene butyl rubber, polybutadiene rubber, acrylate rubber, polychloroprenerubber, acrylonitrile butadiene. Acrylonitrile butadiene rubber, styrene butadiene rubber or ethylene copolymers. The method for producing a foamed thermoplastic vulcan material according to any one of claims 2 to 4, wherein in the step of dynamically vulcanizing and foaming the foamable thermoplastic vulcan composition, the foamable thermoplastic vulcan composition The elastomer is an ethylene copolymer, and the ethylene copolymer is an ethylene-olefin copolymer, an ethylene propylene diene monomer rubber, an ethylene vinyl acetate or an ethylene. Ethylene glycidyl methacrylate. The method for producing a foamed thermoplastic vulcan material according to any one of claims 2 to 4, wherein in the step of dynamically vulcanizing and foaming the foamable thermoplastic vulcan composition, the foamable thermoplastic vulcan composition The thermoplastic is a homopolymer or copolymer of propylene, a homopolymer or copolymer of ethylene, a homopolymer or copolymer of butadiene. , a homopolymer or copolymer of isoprene, a homopolymer or copolymer of styrene, a homopolymer or copolymer of acrylonitrile, polymethyl methacrylate Poly(methyl methacrylate), polyamide, polylactic acid, polycarbonate or a mixture thereof. The method for producing a foamed thermoplastic vulcan material according to any one of claims 2 to 4, wherein in the step of dynamically vulcanizing and foaming the foamable thermoplastic vulcanizate, the foamable thermoplastic vulcan is comprised The total weight of the material is 100%, and the weight percentage of the crosslinked phase composed of the expandable thermoplastic sulfide is 55 to 90%. The method for producing a foamed thermoplastic vulcan material according to any one of claims 2 to 4, wherein in the step of dynamically vulcanizing and foaming the foamable thermoplastic vulcanizate, the foamable thermoplastic vulcan is comprised The total weight of the material is 100%, and the weight percentage of the matrix phase of the foamable thermoplastic sulfide composition is 10 to 45%. The method for producing a foamed thermoplastic vulcan material according to any one of claims 2 to 4, wherein the foamed thermoplastic vulcan material obtained by the step of dynamically vulcanizing and foaming the expandable thermoplastic vulcan composition The density is greater than or equal to 0.05 g/cm ³ . The method for producing a foamed thermoplastic vulcan material according to any one of claims 2 to 4, wherein the foamed thermoplastic vulcan material obtained by the step of dynamically vulcanizing and foaming the expandable thermoplastic vulcan composition The density is greater than or equal to 0.10 g/cm 3 . The method for producing a foamed thermoplastic vulcan material according to any one of claims 2 to 4, wherein the foamed thermoplastic vulcan material obtained by the step of dynamically vulcanizing and foaming the expandable thermoplastic vulcan composition The density is greater than or equal to 0.20 g/cm 3 . A method for producing a foamed thermoplastic vulcanizate article, comprising: treating a foamed thermoplastic vulcanized material obtained according to any one of claims 2 to 26 by a thermoplastic method to form The foamed thermoplastic vulcanizate product. The method for producing a foamed thermoplastic vulcanizate according to claim 27, wherein the foamed thermoplastic vulcan material is treated by a thermoplastic method by injection molding, thermoforming, extrusion molding (extrusion molding) Molding) or melting. The method for producing a foamed thermoplastic vulcanizate according to any one of claims 27 to 28, wherein the foamed thermoplastic vulcanizate has a density of greater than or equal to 0.05 g/cm 3 . The method for producing a foamed thermoplastic vulcanizate according to any one of claims 27 to 28, wherein the foamed thermoplastic vulcanizate has a density of greater than or equal to 0.10 g/cm 3 . The method for producing a foamed thermoplastic vulcanizate according to any one of claims 27 to 28, wherein the foamed thermoplastic vulcanizate has a density of greater than or equal to 0.20 g/cm 3 . A method of producing a foamed thermoplastic vulcanizate comprising: preparing a foamable thermoplastic vulcanization composition; dynamically vulcanizing the foamable thermoplastic vulcanization composition to form a foamable thermoplastic vulcanic material; and then simultaneously Foaming and thermoplastically treating the foamable thermoplastic vulcan material to form a foamed thermoplastic vulcanizate; wherein the foamable thermoplastic vulcanizate comprises a crosslinked phase, a matrix phase and a blowing agent The crosslinked phase comprises an elastomer and a crosslinking agent, and the matrix phase comprises a thermoplastic plastic. The method of producing a foamed thermoplastic vulcanizate according to claim 32, wherein the foamed thermoplastic vulcanizate has a density of greater than or equal to 0.05 g/cm 3 . The method of producing a foamed thermoplastic vulcanizate according to claim 32, wherein the foamed thermoplastic vulcanizate has a density of greater than or equal to 0.10 g/cm 3 . The method of producing a foamed thermoplastic vulcanizate according to claim 32, wherein the foamed thermoplastic vulcanizate has a density of greater than or equal to 0.20 g/cm 3 .