CN113462044A - Composite embossed flexible foam material and preparation method thereof - Google Patents

Composite embossed flexible foam material and preparation method thereof Download PDF

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Publication number
CN113462044A
CN113462044A CN202110788011.0A CN202110788011A CN113462044A CN 113462044 A CN113462044 A CN 113462044A CN 202110788011 A CN202110788011 A CN 202110788011A CN 113462044 A CN113462044 A CN 113462044A
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rubber
composite
embossed
layer
plasticizer
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CN202110788011.0A
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CN113462044B (en
Inventor
高贺勇
高贺昌
吴华明
何兵
郭超
崔建坡
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Huamei Energy Saving Technology Jiangxi Co ltd
Huamei Energy Saving Technology Group Co ltd
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Huamei Energy Saving Technology Jiangxi Co ltd
Huamei Energy Saving Technology Group Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/102—Azo-compounds
    • C08J9/103—Azodicarbonamide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
    • B32B37/153—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/06—Embossing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/32—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed at least two layers being foamed and next to each other
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B2038/0052—Other operations not otherwise provided for
    • B32B2038/0084—Foaming
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0207—Materials belonging to B32B25/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/304—Insulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/582—Tearability
    • B32B2307/5825—Tear resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08J2309/02—Copolymers with acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2315/00—Characterised by the use of rubber derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
    • C08J2323/28—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by reaction with halogens or halogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2327/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2411/00—Characterised by the use of homopolymers or copolymers of chloroprene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
    • C08J2423/28—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by reaction with halogens or halogen-containing compounds
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
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    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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Abstract

The invention discloses a composite embossed flexible foaming material and a preparation method thereof, wherein the composite embossed flexible foaming material consists of an embossed layer and a heat-insulating layer and comprises a framework material, a filler, a foaming agent, a cross-linking agent, an accelerant, an active agent, a plasticizer, a lubricant, a flame retardant, a compatilizer, a reinforcing agent, a pigment and the like. The framework material is composed of nitrile rubber, polyvinyl chloride paste resin, chlorinated polyethylene and a tear-resistant polymer. The composite embossed flexible foaming material adopts a continuous production process of co-mixing extrusion and vulcanization foaming integrated molding of two extruders, and has simple and convenient production and manufacturing process and high efficiency; in addition, besides the heat preservation performance of the original foam material is guaranteed, the tear-resistant embossed layer is endowed with corresponding functions by selecting raw materials with good tear resistance or adjusting the formula proportion, so that the requirements of attractiveness and difficulty in scratching and cracking in the construction process are met.

Description

Composite embossed flexible foam material and preparation method thereof
Technical Field
The invention belongs to the technical field of high polymer material foaming, and particularly relates to a composite embossed flexible foaming material and a preparation method thereof.
Background
The traditional NBR/PVC rubber-plastic foaming thermal insulation material is difficult to meet the requirements of different customers and some engineering and construction aspects, such as appearance aesthetic property, color, surface tearing strength and the like. The currently applied products comprise two types, one is a traditional foamed product formed by single color and single sizing material, such as CN103102533A, and the defects of single structure, insufficient integral aesthetic degree, poor skin tearing property and the like exist. In the other method, a composite layer with other colors is adhered on the surface layer of the traditional rubber-plastic heat-insulating material in an adhesive mode, the mode has high processing cost, complicated procedures, irregular veneering and low composite strength, and the used binder has great harm to the environment, thereby influencing the overall aesthetic property and the environmental protection property of the rubber-plastic heat-insulating material.
Patent CN203974373U and patent CN 204236121U disclose respectively "a relief craft rubber and plastic heated board" and "a relief figure flexible rubber and plastic foamed heated board", but the general rubber and plastic relief board still has the defect that the surface tearing strength is poor in some specific application fields, the outward appearance is not bright-colored beautiful, pleasing to the eye visual difference. CN108892825A discloses 'a multilayer composite rubber-plastic foam heat-insulation material and a preparation method', the composite rubber-plastic foam heat-insulation material prepared by the process method has the defects of no concave-convex layer on the surface, no beauty, influence on decoration and sound absorption effects and the like; and the manufacturing and forming are oven foaming, which is not continuous forming, and the production efficiency is low.
Disclosure of Invention
Aiming at the defects of the traditional rubber-plastic foaming heat-insulating material in the prior art, the invention aims to provide the composite embossed flexible foaming material which has high surface tearing strength, bright and beautiful appearance and good beautiful vision, and the invention also aims to provide the preparation method of the composite embossed flexible foaming material which is produced by blending extrusion through two extruders and continuous vulcanization foaming.
The composite embossed flexible foaming material is a plate.
The composite embossed flexible foaming material consists of an embossed layer and a heat-insulating layer, wherein the embossed layer and the heat-insulating layer are of an integral structure.
The composite embossed flexible foaming material comprises a framework material, a filler, a foaming agent, a cross-linking agent, an accelerant, an active agent, a plasticizer, a lubricant, a flame retardant, a compatilizer, a reinforcing agent, a pigment and the like.
The framework material comprises nitrile rubber, polyvinyl chloride paste resin and chlorinated polyethylene.
The polyvinyl chloride paste resin adopted by the invention is more beneficial to material foaming, has lower plasticizing temperature and better dispersion effect, and ensures that the final product has high tearing strength, good flexibility and good apparent quality. And different from the NBR/PVC system in the prior art, the formula system of the polyvinyl chloride paste resin has mild processing conditions, saves more energy in the processing process and reduces the energy consumption.
The polyvinyl chloride paste resin of the heat preservation layer accounts for 6-11 parts by weight of the formula of the heat preservation layer in the composite embossed flexible foaming material.
The embossed layer polyvinyl chloride paste resin accounts for 4-8 parts by weight of the embossed layer formula in the composite embossed flexible foam material.
The heat-insulating layer chlorinated polyethylene accounts for 4-9 parts by weight of the formula of the heat-insulating layer in the composite embossed flexible foaming material.
The embossing layer chlorinated polyethylene accounts for 3-7 parts by weight of the embossing layer formula in the composite embossing flexible foam material.
Furthermore, the framework material of the embossed layer also comprises a tear-resistant polymer, and the proportion of the tear-resistant polymer is adjusted by the tear-resistant embossed layer according to the requirements of products.
The anti-tearing polymer of the embossed layer accounts for 10-25 parts by weight of the formula of the embossed layer in the composite embossed flexible foam material.
The tear-resistant polymer is one of epoxidized natural rubber ENR, chloroprene rubber CR and polyester type thermoplastic elastomer TPEE or polyurethane rubber PUR.
The tear-resistant polymer comprises the following components in parts by weight: epoxidized natural rubber ENR: 20-90, chloroprene rubber CR: 5-30, and a polyester type thermoplastic elastomer TPEE or polyurethane rubber PUR: 5-50.
Preferably, the weight parts of each component in the tear-resistant polymer are respectively epoxidized natural rubber ENR: 50-60, chloroprene rubber CR: 10-20, and a polyester type thermoplastic elastomer TPEE or polyurethane rubber PUR: 20-30.
The filler is selected from talcum powder, aluminum hydroxide, calcium carbonate and the like.
The foaming agent is azodicarbonamide and the like.
The cross-linking agent is sulfur and the like.
The accelerator is 2-3 of dimethyl dithiocarbamate (PZ), dipentamethylenethiuram tetrasulfide (DPTT), accelerator D (diphenyl guanidine) and accelerator M (2-mercaptobenzothiazole).
The active agent is composed of nano zinc oxide, zinc p-toluenesulfinate and the like.
The plasticizer is composed of epoxidized soybean oil and one of chlorinated paraffin oil and dioctyl sebacate (DOS).
The embossed layer dioctyl sebacate (DOS) accounts for 18-24 parts by weight of the embossed layer formula in the composite embossed flexible foam material.
The lubricant is selected from the group consisting of fully refined paraffin, stearic acid, polyethylene glycol, and the like.
The flame retardant is antimony trioxide and the like.
The compatilizer can enhance the compatibility among polymers and increase the interfacial adhesion force among composite materials, thereby improving the tear resistance of the embossing layer material. The compatilizer is maleic anhydride grafted PE and the like, the heat-insulating layer is not added with the compatilizer, and the dosage of the compatilizer is adjusted according to the product requirement by the tear-resistant embossed layer.
The embossed layer maleic anhydride grafted PE comprises 1-3 parts by weight of the embossed layer formula in the composite embossed flexible foam material.
The reinforcing agent is carbon black or titanium dioxide and the like.
The pigment is an inorganic pigment or an organic pigment, and the pigment is only added into the embossing layer.
The composite embossed flexible foaming material comprises the following components in parts by weight as shown in the following table 1:
table 1: formula table of heat-insulating layer and embossed layer
Figure BDA0003159752180000031
Figure BDA0003159752180000041
Further, the invention provides a preparation method of the composite embossed flexible foam material, which comprises the following steps:
a) and preparing a sizing material of the heat-insulating layer and the embossing layer.
Firstly, preparing an insulating layer sizing material.
The raw materials are weighed according to the proportion, the filler and the plasticizer are respectively divided into two parts, the weight ratio of the first part of filler to the second part of filler is 1-3:1, and the weight ratio of the first part of plasticizer to the second part of plasticizer is 1-3: 1.
Preferably, the weight ratio of the first part by weight of filler to the second part by weight of filler is 2:1, and the weight ratio of the first part by weight of plasticizer to the second part by weight of plasticizer is 2: 1.
The filler is selected from talcum powder, aluminum hydroxide and the like.
The first portion of filler is preferably aluminum hydroxide.
The plasticizer is epoxidized soybean oil, chlorinated paraffin oil and the like.
The first portion of plasticizer is preferably chlorinated paraffin oil.
Mixing the framework material, the first part of filler, the plasticizer, other fillers, the plasticizer, the lubricant, the flame retardant, the reinforcing agent and the like which are weighed according to the proportion, putting the mixed raw materials into an internal mixer for internal mixing for 5-10min, then adding the second part of filler and the plasticizer for continuous mixing for 3-5 min; the temperature of banburying rubber mixing is 140-170 ℃. And finally, putting the internally mixed rubber material into an open mill for open milling for 5-15min, and cooling and slicing to obtain No. 1 rubber material.
And (2) putting the foaming agent, the cross-linking agent, the accelerator, the activator and the No. 1 rubber material which are weighed according to the proportion into an open mill for open milling for 8-15min, wherein the open milling rubber mixing temperature is 35-60 ℃, and then cooling and slitting to obtain the heat-insulation layer rubber material.
② preparing an embossing layer sizing material.
The raw materials are weighed according to the proportion, the filler and the plasticizer are respectively divided into two parts, the weight ratio of the first part of filler to the second part of filler is 1-3:1, and the weight ratio of the first part of plasticizer to the second part of plasticizer is 1-3: 1.
Preferably, the weight ratio of the first part by weight of filler to the second part by weight of filler is 2:1, and the weight ratio of the first part of plasticizer to the second part of plasticizer is 2: 1.
The filler is selected from talcum powder, aluminum hydroxide, calcium carbonate and the like.
The first portion of filler is preferably aluminum hydroxide.
The plasticizer is epoxidized soybean oil, dioctyl sebacate (DOS) and the like.
The first portion of plasticizer is preferably dioctyl sebacate (DOS).
Mixing the framework material, the first part of filler, the plasticizer, other fillers, the plasticizer, the lubricant, the flame retardant, the compatilizer, the reinforcing agent, the pigment and the like which are weighed according to the proportion, putting the mixed raw materials into an internal mixer for internal mixing for 5-10min, then adding the second part of filler and the plasticizer for continuous mixing for 3-5 min; the temperature of banburying rubber mixing is 150-190 ℃. And finally, putting the internally mixed rubber material into an open mill for open milling, wherein the open milling time is 5-15min, the open milling rubber temperature is 35-60 ℃, and then cooling and slicing to obtain No. 2 rubber material.
And (3) putting the foaming agent, the cross-linking agent, the accelerant, the active agent and the No. 2 sizing material which are weighed according to the proportion into an open mill for open milling for 8-15min, and then cooling and slitting to obtain the embossing layer sizing material.
b) And respectively feeding the heat-insulating layer and the embossed layer rubber material into an extruder integrated composite device for extrusion molding, and then embossing by using an embossed embossing roller. The extruder integrated composite device is an integral device formed by connecting two extruders with a neck ring mold.
c) And (4) the molded film subjected to embossing treatment enters an automatic production line for continuous foaming production.
d) And finally, cooling and shaping the composite embossed flexible foam material by a cooling frame to obtain the composite embossed flexible foam material.
According to the preparation method, in the step b), the anti-tear embossed beautiful layer and the heat-insulating layer are both flat plates during blending and extrusion.
According to the preparation method, in the step b), the parameters of the extruder are as follows: the temperature of the screw of the extruder is 25-50 ℃, wherein the temperature of the feeding section is 25-40 ℃, the temperature of the plasticizing section is 40-50 ℃, and the temperature of the machine head section is 35-50 ℃.
The extruder pressure is usually controlled to be 0.2 to 0.6MPa, and specifically, it is preferably: the pressure of the feeding section is 0.2-0.4MPa, the pressure of the plasticizing section is 0.5-0.6MPa, and the pressure of the machine head is 0.5-0.6 MPa.
The forming die in the step b) comprises a first die and a second die, the first die extrudes the heat-insulating layer rubber material, the second die extrudes the anti-tearing embossing layer, and the material attaching structure is formed between the first die and the second die through a die runner. The first die and the second die in the die are of a composite integrated structure, and a flow channel and a forming area are shared in the composite structure, so that the embossing layer and the heat-insulating layer form an integral structure without separation.
The embossing roll in the step b) is of a double-roll structure subjected to the embedding and carving processing, and the embossing pattern can be specially designed according to the requirement.
In the step c), the foaming temperature of the foaming furnace is preferably controlled to be 60-100 ℃ and the outlet temperature is preferably controlled to be 155-160 ℃.
In the step c), the foaming process is to continuously feed the extruded film into a foaming furnace, and perform foaming treatment in 6 foaming zones in sequence, wherein the transmission speed is 1-1.4m/min in the first zone, 1.2-1.5m/min in the second zone, 1.5-1.7m/min in the third zone, 2.5-3.2m/min in the fourth zone, 3.7-4.7m/min in the fifth zone, and 5.0-7.0m/min in the sixth zone.
The temperature of each area of the foaming furnace is respectively as follows: the first zone is 80-110 ℃, the second zone is 100-.
Compared with the prior art, the composite embossed flexible foam material and the preparation method thereof have the following advantages:
1. the polyvinyl chloride paste resin is introduced into the formula of the composite embossed flexible foaming material, so that the material is more favorable for foaming, and the material has lower plasticizing temperature and better dispersion effect, so that the final product has high tearing strength, good flexibility and good apparent quality.
2. Chlorinated polyethylene CPE base materials are introduced into the formula of the composite embossed flexible foaming material, so that the comprehensive performance of the rubber-plastic composite foaming system is greatly improved. In the aspect of vulcanization characteristics, with the addition of CPE, the elasticity, viscosity and crosslinking effect of the rubber-plastic blended rubber are improved, compared with a formula without CPE, the Mooney value of the rubber material can be improved by 1-3, the vulcanization value is improved by 0.1-0.3, and the improvement of the foaming performance of the rubber material in the formula is facilitated; in the aspect of mechanical property, with the addition of CPE, the compression elasticity, tearing strength and the like of the rubber-plastic foaming material are improved.
3. The composite embossed flexible foaming material disclosed by the invention is foamed by selecting a rubber-plastic blended material and adding an elastomer material with high tearing strength, and exceeds the limitation of foaming by selecting the rubber-plastic blended material in the prior art.
4. The embossing layer adopts dioctyl sebacate (DOS) as a plasticizer, so that the product has good plasticizing effect, low volatility and good product flexibility.
5. The compatilizer maleic anhydride grafted PE is added into the formula of the composite embossed flexible foaming material, so that the problem that the compatibility of the composite embossed flexible foaming material with the original base material is reduced when a nonpolar polymer with better tearing strength is selected is solved, the binding force among the base materials is obviously improved after the compatilizer maleic anhydride grafted PE is added, and the comprehensive performance of the product is greatly improved.
6. Compared with the common multilayer composite manufacturing process in the prior art, in the preparation method of the composite embossed flexible foam material, the preparation processes of the anti-tear embossed layer and the heat-insulating layer rubber material are the same, and the embossed layer and the heat-insulating layer rubber material adopt the composite extrusion integrated manufacturing process of two screw extruders, so that the foam material can be compounded in multiple layers, the online continuous production is realized, and the technical performance of the embossed product is improved.
7. According to the invention, through optimizing the formula, the low open mixing temperature in the preparation process of the composite embossing flexible foaming material is realized, the temperature of the inlet and the outlet of the foaming furnace is low, the processing conditions are mild, the processing process is more energy-saving, and the energy consumption is reduced.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments and examples, and the advantages and various effects of the present invention will be more clearly apparent therefrom. It will be understood by those skilled in the art that these specific embodiments and examples are for the purpose of illustrating the invention and are not to be construed as limiting the invention.
The composite embossed flexible foam material is composed of a tear-resistant embossed layer and a heat insulation layer, wherein the tear-resistant embossed layer and the heat insulation layer are both made of flexible foam materials, the tear-resistant embossed layer and the heat insulation layer are integrally formed through blending extrusion and vulcanization foaming, and the tear-resistant embossed attractive layer and the heat insulation layer are of an integral structure.
Various pigments with different colors can be added into the anti-tearing embossed layer according to the requirements so as to meet different requirements.
Comparative example 1 a composite embossed flexible foamed material was prepared using the preparation method of the present invention using the formulation of CN108892825A example 2.
The formulations of the examples are shown in table 2 below.
Table 2: examples 1-4 formulations, in parts by weight.
Figure BDA0003159752180000071
Figure BDA0003159752180000081
In Table 2, the types and the amount ratios of the tear-resistant polymers are shown in Table 3.
Table 3: examples 1-4 types and ratios of tear resistant polymers.
Species of Example 1 Example 2 Example 3 Example 4
ENR 60％ 60％ 50％ 50％
TPEE 20％ 30％ - -
PUR - - 30％ 30％
CR 20％ 10％ 20％ 20％
Table 4: examples 1-4 and comparative example 1 performance test results.
Figure BDA0003159752180000091
As can be seen from Table 4, the invention solves the problem that the compatibility of the non-polar polymer with better tear strength with the original base material is reduced by optimizing the formula, ensures that the product has higher tear strength, compression rebound rate and wet resistance factor, and greatly improves the comprehensive performance of the product.

Claims (10)

1. A composite embossed flexible foam material comprises an embossed layer and a heat-insulating layer, and comprises a framework material, a filler, a foaming agent, a cross-linking agent, an accelerant, an active agent, a plasticizer, a lubricant, a flame retardant, a compatilizer, a reinforcing agent and a pigment, and is characterized in that the framework material comprises nitrile rubber, polyvinyl chloride paste resin and chlorinated polyethylene.
2. The composite embossed flexible foamed material according to claim 1, wherein the embossed layer skeleton material further comprises a tear-resistant polymer.
3. The composite embossed flexible foamed material according to claim 2, wherein the tear-resistant polymer is one of epoxidized natural rubber ENR, chloroprene rubber CR, and polyester type thermoplastic elastomer TPEE or polyurethane rubber PUR.
4. The composite embossed flexible foamed material according to claim 3, wherein the tear-resistant polymer comprises the following components in parts by weight: epoxidized natural rubber ENR: 20-90, chloroprene rubber CR: 5-30, and a polyester type thermoplastic elastomer TPEE or polyurethane rubber PUR: 5-50; preferably, the weight parts of the epoxidized natural rubber ENR: 50-60, chloroprene rubber CR: 10-20, and a polyester type thermoplastic elastomer TPEE or polyurethane rubber PUR: 20-30.
5. The composite embossed flexible foamed material according to any one of claims 1 to 4, wherein the compatibilizer is maleic anhydride grafted PE.
6. The method for preparing the composite embossed flexible foamed material according to any one of claims 1 to 5, comprising the following steps:
a) preparing a sizing material of the heat-insulating layer and the embossing layer;
firstly, preparing a heat-insulating layer sizing material; weighing raw materials in proportion, and dividing the filler and the plasticizer into two parts respectively;
mixing the framework material, the first part of filler, the plasticizer, other fillers, the plasticizer, the lubricant, the flame retardant and the reinforcing agent which are weighed according to the proportion, putting the mixed raw materials into an internal mixer for banburying, and then adding the second part of filler and the plasticizer for continuous rubber mixing; finally, putting the internally mixed rubber material into an open mill for open milling, and then cooling and slicing to obtain No. 1 rubber material;
putting the foaming agent, the cross-linking agent, the accelerant, the active agent and the No. 1 sizing material which are weighed according to the proportion into an open mill for open milling, and then cooling and slitting to obtain a sizing material of the heat-insulating layer;
preparing an embossing layer sizing material;
weighing raw materials in proportion, and dividing the filler and the plasticizer into two parts respectively;
mixing the framework material, the first part of filler, the plasticizer, other fillers, the plasticizer, the lubricant, the flame retardant, the compatilizer, the reinforcing agent and the pigment which are weighed according to the proportion, putting the mixed raw materials into an internal mixer for internal mixing, and then adding the second part of filler and the plasticizer for continuous mixing; finally, putting the internally mixed rubber material into an open mill for open milling, and then cooling and slicing to obtain No. 2 rubber material;
putting the foaming agent, the cross-linking agent, the accelerant, the active agent and the No. 2 sizing material which are weighed according to the proportion into an open mill for open milling, and then cooling and slitting to obtain an embossing layer sizing material;
b) feeding the heat-insulating layer and the embossed layer rubber material into an extruder integrated composite device respectively for extrusion molding, and then embossing by an embossed embossing roller;
c) the molded film after embossing treatment enters an automatic production line for continuous foaming production;
d) and finally, cooling and shaping the composite embossed flexible foam material by a cooling frame to obtain the composite embossed flexible foam material.
7. The method for preparing the composite embossed flexible foamed material according to claim 6, wherein the open mixing temperature of the No. 1 rubber compound and the No. 2 rubber compound is 35-60 ℃.
8. The method for preparing the composite embossed flexible foamed material according to the claim 6 or 7, wherein the extruder-integrated composite device is an integrated device of two extruders connected with a die.
9. The method for preparing the composite embossed flexible foamed material according to any one of claims 6 to 8, wherein the forming mold in the step b) comprises a first mold and a second mold, the first mold extrudes the heat insulation layer rubber material, the second mold extrudes the tear-resistant embossed layer, and the first mold and the second mold form a material attaching structure through a mold runner.
10. The method for preparing the composite embossed flexible foamed material according to any one of claims 6 to 9, wherein in the step c), the foaming temperature of the foaming furnace is controlled to be 60 to 100 ℃ and the outlet temperature is controlled to be 155 ℃ and 160 ℃.
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Publication number Priority date Publication date Assignee Title
US3772138A (en) * 1966-08-16 1973-11-13 Armstrong Cork Co Chemically embossed surface coverings using barrier film
CN109294015A (en) * 2018-09-17 2019-02-01 常州广裕橡塑科技有限公司 Continuous pore rubber and plastic slow-rebound foaming material and preparation method thereof
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CN110684244A (en) * 2019-10-12 2020-01-14 福建五持恒科技发展有限公司 Graphene natural rubber foamed polymer composite material and preparation method thereof
CN112552562A (en) * 2020-12-14 2021-03-26 深圳市乐普泰科技股份有限公司 Ultralow temperature resistant rubber foam material and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3772138A (en) * 1966-08-16 1973-11-13 Armstrong Cork Co Chemically embossed surface coverings using barrier film
CN109294015A (en) * 2018-09-17 2019-02-01 常州广裕橡塑科技有限公司 Continuous pore rubber and plastic slow-rebound foaming material and preparation method thereof
CN110256837A (en) * 2019-04-28 2019-09-20 东莞华工佛塑新材料有限公司 A kind of composition and preparation method thereof being used to prepare wear-resisting waterproof high resiliency foamed material
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