CN116589807B - Heat-resistant PVC film and preparation method and application thereof - Google Patents

Heat-resistant PVC film and preparation method and application thereof Download PDF

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CN116589807B
CN116589807B CN202310868739.3A CN202310868739A CN116589807B CN 116589807 B CN116589807 B CN 116589807B CN 202310868739 A CN202310868739 A CN 202310868739A CN 116589807 B CN116589807 B CN 116589807B
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heat
pvc
resistant
parts
film
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CN116589807A (en
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张翔
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Guangzhou Renolit Plastic Co ltd
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Guangzhou Renolit Plastic 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • 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
    • 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
    • C08J2425/00—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 an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2425/02—Homopolymers or copolymers of hydrocarbons
    • C08J2425/04—Homopolymers or copolymers of styrene
    • C08J2425/08—Copolymers of styrene
    • 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
    • C08J2425/00—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 an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2425/02—Homopolymers or copolymers of hydrocarbons
    • C08J2425/04—Homopolymers or copolymers of styrene
    • C08J2425/08—Copolymers of styrene
    • C08J2425/12—Copolymers of styrene with unsaturated nitriles
    • 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
    • C08J2433/00—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • 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
    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • 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
    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • 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
    • C08J2455/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2423/00 - C08J2453/00
    • C08J2455/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
    • 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
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
    • Y02A40/25—Greenhouse technology, e.g. cooling systems therefor

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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Abstract

The application provides a heat-resistant PVC film, and a preparation method and application thereof. The raw materials of the heat-resistant PVC film at least comprise PVC resin, a heat-resistant modifier and a compatilizer; the addition amount of the heat-resistant modifier is 5-50% of the weight of the PVC resin, and the addition amount of the compatilizer is 5-40% of the weight of the PVC resin. The preparation method of the heat-resistant PVC film comprises the following steps: and mixing the raw materials except the heat-resistant modifier and the compatilizer to obtain a premix, and blending the premix, the heat-resistant modifier and the compatilizer to prepare the film. The application provides application of the heat-resistant PVC film in preparing decorative materials and building materials. The PVC film has excellent heat resistance, good compatibility, processing and surface properties, and provides more selection space for processing and application of the PVC film.

Description

Heat-resistant PVC film and preparation method and application thereof
Technical Field
The application relates to the technical field of high polymer materials, in particular to a heat-resistant PVC film and a preparation method and application thereof.
Background
Polyvinyl chloride (PVC) is a polymer obtained by polymerizing Vinyl Chloride Monomer (VCM) under the action of an initiator such as peroxide or azo compound or light or heat by a radical polymerization mechanism. Vinyl chloride homopolymers and vinyl chloride copolymers are collectively referred to as vinyl chloride treesAnd (3) grease. The molecular weight of the PVC produced in industry is generally in the range of 5 ten thousand to 11 ten thousand, has larger polydispersibility, the molecular weight is increased along with the reduction of the polymerization temperature, has no fixed melting point, begins to soften at 80 to 85 ℃, changes into a viscoelastic state at 130 ℃ and begins to change into a viscous fluid state at 160 to 180 ℃; has better mechanical property, about 60MPa of tensile strength and 5-10 kJ/m of impact strength 2 The method comprises the steps of carrying out a first treatment on the surface of the Has excellent dielectric properties. PVC has excellent comprehensive performance and outstanding cost performance, so that the PVC has wide application in various industries, particularly as a decorative material, has rich colors and strong adaptability in various processing and post-treatment modes, and is dominant in the field of house decorative films. However, the heat resistance of the PVC film on the market is not good, but some subsequent processing and application (such as cutting, polishing, stamping and other processes after the plate is pasted on the film) place higher demands on the heat resistance of the PVC film, so that it is necessary to provide a heat-resistant PVC film to further cope with the heat resistance demands of the PVC film on the market.
Disclosure of Invention
The application aims to provide a heat-resistant PVC film, a preparation method and application thereof, so as to enhance the heat resistance of the PVC film and meet the higher quality requirements of the market on the PVC film.
In order to achieve the technical purpose, the application adopts the following technical scheme:
in a first aspect, the present application provides a heat-resistant PVC film, the raw materials of which include at least a PVC resin, a heat-resistant modifier and a compatibilizer; the addition amount of the heat-resistant modifier is 5-50% of the weight of the PVC resin, and the addition amount of the compatilizer is 5-40% of the weight of the PVC resin.
Preferably, the heat resistant modifier is selected from at least one of MS-NI, SAN, ABS, TPU; preferably, the addition amount of the heat-resistant modifier is 10-30% of the weight of the PVC resin.
Preferably, the compatilizer is at least one selected from ABS-g-MAH, PVC-g-MAH, PP-g-ST, PE-g-ST and PP-g-MAH; preferably, the addition amount of the compatilizer is 5-20% of the weight of the PVC resin.
Preferably, the raw materials of the PVC film further comprise a plasticizer, and the addition amount of the plasticizer is 6-25% of the weight of the PVC resin.
Preferably, the plasticizer comprises a primary plasticizer and a secondary plasticizer, the primary plasticizer is selected from at least one of diisononyl phthalate (DINP), dioctyl phthalate (DOP), didecyl phthalate (DPHP); further preferably, the addition amount of the primary plasticizer is 6-20% of the weight of the PVC resin; the auxiliary plasticizer is at least one selected from Epoxidized Soybean Oil (ESO) and dioctyl adipate (DOA); further preferably, the addition amount of the auxiliary plasticizer is 0-5% of the weight of the PVC resin.
Preferably, the raw material of the PVC film further comprises a stabilizer, wherein the stabilizer is at least one selected from an organotin stabilizer, a Ba/Zn stabilizer and a Ca/Zn stabilizer; preferably, the addition amount of the stabilizer is 2-5% of the weight of the PVC resin.
Preferably, the raw materials of the PVC film further comprise a processing aid, wherein the processing aid is at least one selected from ACR and methyl Methacrylate (MBS); preferably, the addition amount of the processing aid is 0-3% of the weight of the PVC resin.
Preferably, the raw materials of the PVC film further comprise a lubricant, wherein the lubricant is at least one selected from oxidized polyethylene wax, sodium stearate and pentaerythritol ester; preferably, the addition amount of the lubricant is 0.5-2% of the weight of the PVC resin.
Preferably, the raw materials of the PVC film comprise PVC resin, a heat-resistant modifier, a compatilizer, a primary plasticizer, a secondary plasticizer, a stabilizer, a processing aid and a lubricant; further preferably, the addition amounts of the heat-resistant modifier, the compatilizer, the primary plasticizer, the secondary plasticizer, the stabilizer, the processing aid and the lubricant are respectively 10-30%, 8-20%, 6-20%, 0.5-5%, 2-5%, 0.5-3% and 0.5-2% of the weight of the PVC resin.
Further preferably, the addition amounts of the heat-resistant modifier, the compatilizer, the primary plasticizer, the secondary plasticizer, the stabilizer, the processing aid and the lubricant are 20-30%, 15-20%, 10-20%, 1-3%, 2-4%, 2-3% and 1-2% of the weight of the PVC resin respectively.
In a second aspect, the present application provides a method for preparing the heat-resistant PVC film described above, comprising: and mixing the raw materials except the heat-resistant modifier and the compatilizer to obtain a premix, and blending the premix, the heat-resistant modifier and the compatilizer to prepare the film.
Preferably, the control parameters for mixing the raw materials other than the heat-resistant modifier and the compatibilizer include: the mixing temperature is 80-100 ℃, the stirring rotation speed is 300-1000rpm, and the mixing time is 10-20 min;
and/or, preferably, the control parameters for blending the premix, the heat resistant modifier, and the compatibilizer include: the mixing temperature is 80-100 ℃, the stirring rotation speed is 300-1000rpm, and the mixing time is 10-20 min.
Preferably, the film is formed by a calendaring process, and further preferably, control parameters of the calendaring process include: the film thickness is 0.03-0.10 mm, the temperature of the calendaring roller is 180-215 ℃, and the temperature of the cooling roller is 40-60 ℃.
Preferably, the raw materials of the PVC film comprise PVC resin, a heat-resistant modifier, a compatilizer, a primary plasticizer, a secondary plasticizer, a stabilizer, a processing aid and a lubricant; the PVC film is prepared by adopting a calendaring system, and the preparation method comprises the following steps:
step 1, heating and blending PVC resin, primary plasticizer, auxiliary plasticizer, stabilizer, processing aid and lubricant in a high-speed mixer, and cooling to obtain premix;
step 2, further blending the premix, the heat-resistant modifier and the compatilizer in a high-speed stirrer to obtain a mixture;
and step 3, preparing the mixture into a film to obtain the heat-resistant PVC film.
Preferably, in the raw materials of the PVC film, the addition amounts of the heat-resistant modifier, the compatilizer, the primary plasticizer, the auxiliary plasticizer, the stabilizer, the processing aid and the lubricant are respectively 10-30%, 8-20%, 6-20%, 0.5-5%, 2-5%, 0.5-3% and 0.5-2% of the weight of the PVC resin.
Further preferably, in the raw materials of the PVC film, the addition amounts of the heat-resistant modifier, the compatilizer, the primary plasticizer, the auxiliary plasticizer, the stabilizer, the processing aid and the lubricant are respectively 20-30%, 15-20%, 10-20%, 1-3%, 2-4%, 2-3% and 1-2% of the weight of the PVC resin.
Preferably, the control parameters of the heating blending in step 1 include: the blending temperature is 80-100 ℃, the stirring rotation speed is 300-1000rpm, and the blending time is 10-20 min;
and/or, the control parameters blended in the step 2 comprise: the blending temperature is 80-100 ℃, the stirring rotation speed is 300-1000rpm, and the blending time is 10-20 min;
and/or, the step 3 of forming the mixture into a film adopts a calendaring process, preferably, the control parameters of the calendaring process comprise: the film thickness is 0.03-0.10 mm, the temperature of the calendaring roller is 180-215 ℃, and the temperature of the cooling roller is 40-60 ℃.
Preferably, the calendaring system comprises a hot mixing unit, a cold mixing unit, an extrusion unit, an open mill unit, a calendaring unit, a cooling unit, a tension unit and a coiling unit which are connected in sequence.
Preferably, the other end of the hot mixing unit is connected with a weighing unit, and the weighing unit is connected with an electromagnetic vibration feeding unit.
Preferably, the number of the open mill units is 2, and the open mill units are connected in series with each other; preferably, the open mill unit is a two-roll open mill.
Preferably, the calendaring unit is connected with the cooling unit through a traction roller and a carrier roller; preferably, the rolling unit is a four-roll calender, and the cooling unit is a cooling roll.
Preferably, the cooling unit and the tension unit are connected through a transmission unit, and a thickness gauge is arranged on the transmission unit.
In a third aspect, the present application provides the use of the heat resistant PVC film described above for the preparation of decorative or construction materials.
In a fourth aspect, the present application provides a decorative material, wherein the surface layer of the decorative material adopts the heat-resistant PVC film.
In a fifth aspect, the present application provides a building material comprising the heat resistant PVC film described above.
The application provides a heat-resistant PVC film which has excellent heat resistance, good compatibility, processing and surface properties and provides more selection space for processing and application of the PVC film.
Drawings
FIG. 1 is a schematic view of a calendaring system, wherein a 1-resin silo; 2-an electromagnetic vibration feeder; 3-weighing machine; 4-a high-speed thermal mixer; 5-a high-speed cold mixer; 6-an extruder or a planetary machine; 7-a first conveyor belt; 8-a two-roll mill; 9-a second conveyer belt; 10-a metal detector; 11-a four-roll calender; 12-pulling rolls; 13-carrier rollers; 14-cooling rollers; 15-thickness gauge; 16-a transmission device; 17-a tension device; 18-center coiler.
Detailed Description
In an embodiment of the application, MS-NI represents styrene-N-phenylmaleimide; SAN represents styrene-acrylonitrile; ABS represents acrylonitrile-butadiene-styrene; TPU means polyurethane; ABS-g-MAH represents maleic anhydride grafted ABS; PVC-g-MAH represents maleic anhydride grafted PVC; PP-g-ST represents styrene grafted PP; PE-g-ST represents styrene grafted PE; PP-g-MAH represents maleic anhydride grafted PP; ACR represents polyacrylate.
As shown in fig. 1, the calendaring system adopted in the embodiment of the application comprises a resin storage bin 1, an electromagnetic vibration feeder 2, a high-speed hot mixer 4, a high-speed cold mixer 5, an extruder 6 (which can be replaced by a planetary machine), two open mills 8 connected in series, a four-roll calendaring machine 11, a cooling roll 14, a tension device 17 and a central coiling machine 18 which are connected in sequence. The other end of the high-speed thermal mixer 4 is connected with a weighing device 3, and the weighing device 3 is connected with an electromagnetic vibration feeder 2. The extruder or planetary machine 6 is connected with two-roll open mills 8 connected in series through a first conveyor belt 7, and the two-roll open mills 8 connected in series through a second conveyor belt 9. The four-roll calender 11 is connected with a cooling roll 14 through a traction roll 12 and a carrier roll 13. The cooling roller 14 and the tension device 17 are connected through a transmission device 16, and a thickness gauge 15 is arranged on the transmission device 16. The above devices are all commercially available devices.
In the description of the present application, it is to be noted that the specific conditions are not specified in examples, and the description is performed under conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The application will now be described in further detail with reference to the drawings and to specific examples, which are given by way of illustration and not limitation.
Example 1
The embodiment provides a heat-resistant PVC film, which is prepared from the following raw materials in parts by weight: 100 parts of emulsion polyvinyl chloride resin (E-PVC), 10 parts of MS-NI, 6 parts of DOP, 6 parts of PVC-g-MAH, 2 parts of organic tin stabilizer, 2 parts of processing aid ACR and 1.3 parts of oxidized polyethylene wax.
The preparation method of the PVC film comprises the following steps:
(1) Weighing the raw materials according to the proportion for standby;
(2) Placing PVC resin, primary plasticizer, stabilizer, processing aid and lubricant into a high-speed mixer, stirring at 80 ℃ for 10min, and cooling to normal temperature to obtain premix;
(3) Blending the premix, the heat-resistant modifier and the compatilizer obtained in the step (2) in a high-speed stirrer at normal temperature for 10min to obtain a mixture;
(4) And (3) preparing the mixture obtained in the step (3) into a film by a calendaring line, thus obtaining the heat-resistant PVC film.
The performance of the PVC film of this example was tested, the bars were placed in acetic acid for 30s, removed and immediately rinsed clean with tap water with a slight blushing of the surface. The PCV film of this example was measured for Heat Distortion Temperature (HDT) =62℃at 0.45MPa according to the standard test method of the ASTM Standard university D648 plastic heat distortion temperature.
Example 2
The embodiment provides a heat-resistant PVC film, which is prepared from the following raw materials in parts by weight: 100 parts of E-PVC resin, 10 parts of DOP, 2 parts of DINP, 20 parts of SAN, 6 parts of PVC-g-MAH, 8 parts of ABS-g-MAH, 3 parts of organotin stabilizer, 2 parts of processing aid MBS and 0.5 part of oxidized polyethylene wax.
The preparation method of the PVC film comprises the following steps:
(1) Weighing the raw materials according to the proportion for standby;
(2) Placing PVC resin, primary plasticizer, stabilizer, processing aid and lubricant into a high-speed mixer, stirring at 90 ℃ for 15min, and cooling to normal temperature to obtain premix;
(3) Blending the premix, the heat-resistant modifier and the compatilizer obtained in the step (2) in a high-speed stirrer at normal temperature for 15min to obtain a mixture;
(4) And (3) preparing the mixture obtained in the step (3) into a film by a calendaring line, thus obtaining the heat-resistant PVC film.
The performance of the PVC film of this example was tested by the same method as in example 1, and the PCV film of this example was tested at 0.45Mpa with hdt=85℃.
Example 3
The embodiment provides a heat-resistant PVC film, which is prepared from the following raw materials in parts by weight: 100 parts of E-PVC resin, 7 parts of SAN, 8 parts of MS-NI, 12 parts of DOP, 6 parts of PVC-g-MAH, 3 parts of ESO, 3 parts of Ba/Zn stabilizer, 2 parts of processing aid ACR and 1 part of oxidized polyethylene wax.
The preparation method of the PVC film comprises the following steps:
(1) Weighing the raw materials according to the proportion for standby;
(2) Placing PVC resin, primary plasticizer, auxiliary plasticizer, stabilizer, processing aid and lubricant into a high-speed mixer, stirring at 90 ℃ for 10min, and cooling to normal temperature to obtain premix;
(3) Blending the premix, the heat-resistant modifier and the compatilizer obtained in the step (2) in a high-speed stirrer at normal temperature for 15min to obtain a mixture;
(4) And (3) preparing the mixture obtained in the step (3) into a film by a calendaring line, thus obtaining the heat-resistant PVC film.
The performance of the PVC film of this example was tested by the same method as in example 1, and the PCV film of this example was tested at 0.45Mpa with hdt=69 ℃.
Example 4
The embodiment provides a heat-resistant PVC film, which is prepared from the following raw materials in parts by weight: 100 parts of E-PVC resin, 7 parts of SAN, 12 parts of DOP, 8 parts of MS-NI, 10 parts of PVC-g-MAH, 3 parts of ESO, 3 parts of Ba/Zn stabilizer, 2 parts of processing aid ACR and 1 part of oxidized polyethylene wax.
The preparation method of the PVC film comprises the following steps:
(1) Weighing the raw materials according to the proportion for standby;
(2) Placing PVC resin, primary plasticizer, auxiliary plasticizer, stabilizer, processing aid and lubricant into a high-speed mixer, stirring at 90 ℃ for 10min, and cooling to normal temperature to obtain premix;
(3) Blending the premix, the heat-resistant modifier and the compatilizer obtained in the step (2) in a high-speed stirrer at normal temperature for 15min to obtain a mixture;
(4) And (3) preparing the mixture obtained in the step (3) into a film by a calendaring line, thus obtaining the heat-resistant PVC film.
The performance of the PVC film of this example was tested by the same method as in example 1, and the PCV film of this example was tested at 0.45Mpa with hdt=67℃.
Example 5
The embodiment provides a heat-resistant PVC film, which is prepared from the following raw materials in parts by weight: 100 parts of E-PVC resin, 15 parts of SAN, 12 parts of DOP, 10 parts of PVC-g-MAH, 3 parts of ESO, 3 parts of Ba/Zn stabilizer, 2 parts of processing aid MBS and 1 part of oxidized polyethylene wax.
The preparation method of the PVC film comprises the following steps:
(1) Weighing the raw materials according to the proportion for standby;
(2) Placing PVC resin, primary plasticizer, auxiliary plasticizer, stabilizer, processing aid and lubricant into a high-speed mixer, stirring at 90 ℃ for 10min, and cooling to normal temperature to obtain premix;
(3) Blending the premix, the heat-resistant modifier and the compatilizer obtained in the step (2) in a high-speed stirrer at normal temperature for 15min to obtain a mixture;
(4) And (3) preparing the mixture obtained in the step (3) into a film by a calendaring line, thus obtaining the heat-resistant PVC film.
The performance of the PVC film of this example was tested by the same method as in example 1, and the PCV film of this example was tested at 0.45Mpa with hdt=81℃.
Example 6
The embodiment provides a heat-resistant PVC film, which is prepared from the following raw materials in parts by weight: 100 parts of E-PVC resin, 10 parts of DOP, 2 parts of DINP, 20 parts of ABS, 6 parts of PVC-g-MAH, 8 parts of ABS-g-MAH, 3 parts of organotin stabilizer, 2 parts of processing aid MBS and 0.5 part of oxidized polyethylene wax. The preparation method is the same as in example 2.
The performance of the PVC film of this example was tested by the same method as in example 1, and the PCV film of this example was tested at 0.45Mpa with hdt=83℃.
Example 7
The embodiment provides a heat-resistant PVC film, which is prepared from the following raw materials in parts by weight: 100 parts of E-PVC resin, 10 parts of DOP, 2 parts of DINP, 20 parts of TPU, 6 parts of PVC-g-MAH, 8 parts of ABS-g-MAH, 3 parts of organotin stabilizer, 2 parts of processing aid MBS and 0.5 part of oxidized polyethylene wax. The preparation method is the same as in example 2.
The performance of the PVC film of this example was tested by the same method as in example 1, and the PCV film of this example was tested at 0.45Mpa with hdt=74℃.
Example 8
The embodiment provides a heat-resistant PVC film, which is prepared from the following raw materials in parts by weight: 100 parts of E-PVC resin, 10 parts of DOP, 2 parts of DINP, 20 parts of SAN, 14 parts of PP-g-ST, 3 parts of organic tin stabilizer, 2 parts of processing aid MBS and 0.5 part of oxidized polyethylene wax. The preparation method is the same as in example 2.
The performance of the PVC film of this example was tested by the same method as in example 1, and the PCV film of this example was tested at 0.45Mpa with hdt=41℃.
Example 9
The embodiment provides a heat-resistant PVC film, which is prepared from the following raw materials in parts by weight: 100 parts of E-PVC resin, 10 parts of DOP, 2 parts of DINP, 20 parts of ABS, 6 parts of PVC-g-MAH, 8 parts of ABS-g-MAH, 3 parts of organotin stabilizer, 2 parts of processing aid MBS and 0.5 part of oxidized polyethylene wax. The preparation method is the same as in example 2.
The performance of the PVC film of this example was tested by the same method as in example 1, and the PCV film of this example was tested at 0.45Mpa with hdt=42℃.
Example 10
The embodiment provides a heat-resistant PVC film, which is prepared from the following raw materials in parts by weight: 100 parts of E-PVC resin, 10 parts of DOP, 2 parts of DINP, 20 parts of ABS, 6 parts of PVC-g-MAH, 8 parts of ABS-g-MAH, 3 parts of organotin stabilizer, 2 parts of processing aid MBS and 0.5 part of oxidized polyethylene wax. The preparation method is the same as in example 2.
The performance of the PVC film of this example was tested by the same method as in example 1, and the PCV film of this example was tested at 0.45Mpa with hdt=45℃.
Example 11
The embodiment provides a heat-resistant PVC film, which is prepared from the following raw materials in parts by weight: 100 parts of E-PVC resin, 10 parts of DOP, 2 parts of DINP, 20 parts of ABS, 6 parts of PVC-g-MAH, 8 parts of ABS-g-MAH, 3 parts of organotin stabilizer, 2 parts of processing aid MBS and 0.5 part of oxidized polyethylene wax. The preparation method is the same as in example 2.
The performance of the PVC film of this example was tested by the same method as in example 1, and the PCV film of this example was tested at 0.45Mpa with hdt=47℃.
Example 12
The embodiment provides a heat-resistant PVC film, which is prepared from the following raw materials in parts by weight: 100 parts of E-PVC resin, 10 parts of DOP, 2 parts of DINP, 20 parts of ABS, 6 parts of PVC-g-MAH, 8 parts of ABS-g-MAH, 3 parts of organotin stabilizer, 2 parts of processing aid MBS and 0.5 part of oxidized polyethylene wax. The preparation method is the same as in example 2.
The performance of the PVC film of this example was tested by the same method as in example 1, and the PCV film of this example was tested at 0.45Mpa with hdt=55℃.
Example 13
The embodiment provides a heat-resistant PVC film, which is prepared from the following raw materials in parts by weight: 100 parts of E-PVC resin, 10 parts of DOP, 2 parts of DINP, 20 parts of SAN, 14 parts of PP-G-MAH, 3 parts of organotin stabilizer, 2 parts of processing aid MBS and 0.5 part of oxidized polyethylene wax. The preparation method is the same as in example 2.
The performance of the PVC film of this example was tested by the same method as in example 1, and the PCV film of this example was tested at 0.45Mpa with hdt=60℃.
Comparative example 1
The embodiment provides a heat-resistant PVC film, which is prepared from the following raw materials in parts by weight: 100 parts of E-PVC resin, 10 parts of DOP, 2 parts of DINP, 6 parts of PVC-g-MAH, 8 parts of ABS-g-MAH, 3 parts of organotin stabilizer, 2 parts of processing aid MBS and 0.5 part of oxidized polyethylene wax. The preparation was the same as in example 2 (except that no heat-resistant modifier was used).
The performance of the PVC film of this example was tested by the same method as in example 1, and the PCV film of this example was tested at 0.45Mpa with hdt=44℃.
Comparative example 2
The embodiment provides a heat-resistant PVC film, which is prepared from the following raw materials in parts by weight: 100 parts of E-PVC resin, 10 parts of DOP, 2 parts of DINP, 20 parts of SAN, 3 parts of organotin stabilizer, 2 parts of processing aid MBS and 0.5 part of oxidized polyethylene wax. The preparation was the same as in example 2 (except that no compatibilizing agent was used).
The performance of the PVC film of this example was tested by the same method as in example 1, and the PCV film of this example was tested at 0.45Mpa with hdt=40℃.
Comparative example 3
The embodiment provides a heat-resistant PVC film, which is prepared from the following raw materials in parts by weight: 100 parts of E-PVC resin, 10 parts of DOP, 2 parts of DINP, 3 parts of organotin stabilizer, 2 parts of processing aid MBS and 0.5 part of oxidized polyethylene wax. The preparation was the same as in example 2 (except that no heat resistant modifier and no compatibilizer were present).
The performance of the PVC film of this example was tested by the same method as in example 1, and the PCV film of this example was tested at 0.45Mpa with hdt=44℃.
TABLE 1 comparison of HDT results for examples 1-13 and comparative examples 1-3
Case (B) PVC Heat-resistant modifier Compatibilizing agent Primary plasticizer Auxiliary plasticizer Stabilizing agent Processing aid Lubricant HDT,℃
Example 1 100 MS-NI 10 PVC-g-MAH 6 DOP 6 / Organotin stabilization Agent 2 Processing aid ACR 2 Oxidized polyethylene wax 1.3 62
Example 2 100 SAN 20 PVC-g-MAH 6，ABS-g-MAH 8 DOP 10，DINP 2 / Organotin stabilization Agent 3 Processing aid MBS 2 Oxidized polyethylene wax 0.5 85
Example 3 100 SAN 7，MS-NI 8 PVC-g-MAH 6 DOP 12 ESO 3 Ba/Zn stabilization Agent 3 Processing aid ACR 2 Oxidized polyethylene wax 1 69
Example 4 100 SAN 7，MS-NI 8 PVC-g-MAH 10 DOP 12 ESO 3 Ba/Zn stabilization Agent 3 Processing aid ACR 2 Oxidized polyethylene wax 1 67
Example 5 100 SAN 15 PVC-g-MAH 10 DOP 12 ESO 3 Ba/Zn stabilization Agent 3 Processing aid MBS 2 Oxidized polyethylene wax 1 81
Example 6 100 ABS 20 PVC-g-MAH 6，ABS-g-MAH 8 DOP 10，DINP 2 / Organotin stabilization Agent 3 Processing aid MBS 2 Oxidized polyethylene wax 0.5 83
Example 7 100 TPU 20 PVC-g-MAH 6，ABS-g-MAH 8 DOP 10，DINP 2 / Organotin stabilization Agent 3 Processing aid MBS 2 Oxidized polyethylene wax 0.5 74
Example 8 100 SAN 20 PP-g-ST 14 DOP 10，DINP 2 / Organotin stabilization Agent 3 Processing aid MBS 2 Oxidized polyethylene wax 0.5 41
Example 9 100 SAN 20 PE-g-ST 14 DOP 10，DINP 2 / Organotin stabilization Agent 3 Processing aid MBS 2 Oxidized polyethylene wax 0.5 42
Examples 10 100 SAN 20 PP-g-MAH 14 DOP 10，DINP 2 / Organotin stabilization Agent 3 Processing aid MBS 2 Oxidized polyethylene wax 0.5 45
Examples 11 100 SAN 20 PVC-g-MAH 6，PP-g-ST 14 DOP 10，DINP 2 / Organotin stabilization Agent 3 Processing aid MBS 2 Oxidized polyethylene wax 0.5 47
Examples 12 100 SAN 20 ABS-g-MAH 8 DOP 10，DINP 2 / Organotin stabilization Agent 3 Processing aid MBS 2 Oxidized polyethylene wax 0.5 55
Examples 13 100 SAN 20 ABS-g-MAH 8PP-G-MAH 14 DOP 10，DINP 2 / Organotin stabilization Agent 3 Processing aid MBS 2 Oxidized polyethylene wax 0.5 60
Comparative example 1 100 / PVC-g-MAH 6，ABS-g-MAH 8 DOP 10，DINP 2 / Organotin stabilization Agent 3 Processing aid MBS 2 Oxidized polyethylene wax 0.5 44
Comparative example 2 100 SAN 20 / DOP 10，DINP 2 / Organotin stabilization Agent 3 Processing aid MBS 2 Oxidized polyethylene wax 0.5 40
Comparative example 3 100 / / DOP 10，DINP 2 / Organotin stabilization Agent 3 Processing aid MBS 2 Oxidized polyethylene wax 0.5 44
Note that: the numbers in the tables indicate the amounts by weight of the corresponding ingredients.
From the data of table 1, examples 1-13 examined the compounding of different heat-resistant modifiers and different compatibilizers, and comparative examples 1-3 examined no heat-resistant modifier, no compatibilizers, and neither, it can be seen that in the present application, when the heat-resistant modifier is selected from at least one of MS-NI, SAN, ABS, TPU, the compatibilizers are selected from at least one of ABS-g-MAH, PVC-g-MAH, and the synergy is generated between the two (examples 1-7), thereby providing the obtained PVC film with excellent heat resistance. In the data in table 1, the heat resistance of the PVC films obtained in example 2, example 5 and example 6 is relatively more prominent, and the HDT value can reach 80 ℃.
The foregoing examples illustrate only a few embodiments of the application and are described in detail herein without thereby limiting the scope of the application. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the application, which are all within the scope of the application. Accordingly, the scope of protection of the present application is to be determined by the appended claims.

Claims (5)

1. A heat resistant PVC film characterized in that: the raw materials at least comprise PVC resin, a heat-resistant modifier and a compatilizer; the addition amount of the heat-resistant modifier is 10-30% of the weight of the PVC resin, and the addition amount of the compatilizer is 5-20% of the weight of the PVC resin; the heat-resistant modifier is selected from one of SAN and ABS; the compatilizer is ABS-g-MAH and PVC-g-MAH;
the PVC film is characterized by further comprising a plasticizer, wherein the addition amount of the plasticizer is 6-25% of the weight of the PVC resin; the plasticizer comprises a primary plasticizer and a secondary plasticizer, wherein the primary plasticizer is at least one selected from diisononyl phthalate (DINP) and dioctyl phthalate (DOP); the addition amount of the primary plasticizer is 6-20% of the weight of the PVC resin; the auxiliary plasticizer is at least one selected from Epoxidized Soybean Oil (ESO) and dioctyl adipate (DOA); the addition amount of the auxiliary plasticizer is 0-5% of the weight of the PVC resin;
the PVC film is characterized in that the raw material of the PVC film further comprises a stabilizer, wherein the stabilizer is at least one selected from an organotin stabilizer, a Ba/Zn stabilizer and a Ca/Zn stabilizer; the addition amount of the stabilizer is 2-5% of the weight of the PVC resin;
the raw materials of the PVC film further comprise a processing aid, wherein the processing aid is at least one selected from ACR and MBS; the addition amount of the processing aid is 0-3% of the weight of the PVC resin;
the raw materials of the PVC film further comprise a lubricant, wherein the lubricant is at least one selected from oxidized polyethylene wax, sodium stearate and pentaerythritol ester; the addition amount of the lubricant is 0.5-2% of the weight of the PVC resin.
2. A heat resistant PVC film according to claim 1, wherein: the PVC film comprises PVC resin, a heat-resistant modifier, a compatilizer, a primary plasticizer, a secondary plasticizer, a stabilizer, a processing aid and a lubricant; the heat-resistant modifier, the compatilizer, the primary plasticizer, the secondary plasticizer, the stabilizer, the processing aid and the lubricant are respectively added in an amount of 10-30%, 8-20%, 6-20%, 0.5-5%, 2-5%, 0.5-3% and 0.5-2% of the weight of the PVC resin.
3. A method for producing a heat-resistant PVC film according to claim 1 or 2, characterized in that: comprising the following steps: and mixing the raw materials except the heat-resistant modifier and the compatilizer to obtain a premix, and blending the premix, the heat-resistant modifier and the compatilizer to prepare the film.
4. A method of producing a heat-resistant PVC film according to claim 3, wherein: the control parameters for mixing the raw materials except the heat-resistant modifier and the compatilizer include: the mixing temperature is 80-100 ℃, the stirring rotation speed is 300-1000rpm, and the mixing time is 10-20 min; and/or, the control parameters for blending the premix, the heat resistant modifier, and the compatibilizer include: the mixing temperature is 80-100 ℃, the stirring rotation speed is 300-1000rpm, and the mixing time is 10-20 min; and/or the number of the groups of groups,
the film is prepared by adopting a calendaring process, and the control parameters of the calendaring process comprise: the film thickness is 0.03-0.10 mm, the temperature of the calendaring roller is 180-215 ℃, and the temperature of the cooling roller is 40-60 ℃;
the PVC film comprises PVC resin, a heat-resistant modifier, a compatilizer, a primary plasticizer, a secondary plasticizer, a stabilizer, a processing aid and a lubricant; the PVC film is prepared by adopting a calendaring system, and the preparation method comprises the following steps:
step 1, heating and blending PVC resin, primary plasticizer, auxiliary plasticizer, stabilizer, processing aid and lubricant in a high-speed mixer, and cooling to obtain premix;
step 2, the premix, the heat-resistant modifier and the compatilizer are further heated and blended in a high-speed stirrer to obtain a mixture;
step 3, preparing the mixture into a film to obtain the heat-resistant PVC film;
the calendaring system comprises a hot mixing unit, a cold mixing unit, an extrusion unit, an open mill unit, a calendaring unit, a cooling unit, a tension unit and a coiling unit which are sequentially connected.
5. Use of the heat-resistant PVC film according to claim 1 or 2 for the preparation of decorative materials or building materials.
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