CN112898673A - PE film and outer composite film with puncture resistance and flame retardance for vacuum insulation panel - Google Patents

PE film and outer composite film with puncture resistance and flame retardance for vacuum insulation panel Download PDF

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CN112898673A
CN112898673A CN202110125203.3A CN202110125203A CN112898673A CN 112898673 A CN112898673 A CN 112898673A CN 202110125203 A CN202110125203 A CN 202110125203A CN 112898673 A CN112898673 A CN 112898673A
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film
flame
vacuum insulation
puncture
flame retardant
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黄世墙
黄汇源
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Liaoning Ke Tu Environmental Protection And Energy Saving Co ltd
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Liaoning Ke Tu Environmental Protection And Energy Saving Co ltd
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B15/00—Layered products comprising a layer of metal
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    • B32—LAYERED PRODUCTS
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    • B32B27/00—Layered products comprising a layer of synthetic resin
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
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    • B32—LAYERED PRODUCTS
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    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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    • 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
    • B32B5/02—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 structural features of a fibrous or filamentary layer
    • 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
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • 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
    • B32B2307/552—Fatigue strength
    • 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
    • B32B2307/558—Impact strength, toughness
    • 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
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/06—Polyethene
    • 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
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/2224—Magnesium hydroxide
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  • Polymers & Plastics (AREA)
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  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

The invention discloses a PE film and an outer layer composite film with puncture resistance and flame retardance for a vacuum heat-insulating plate, and belongs to the technical field of vacuum heat-insulating plates. The PE film is prepared by mixing flame-retardant master batches, linear polyethylene, high-pressure polyethylene and a brominated flame retardant according to a certain proportion and extruding the mixture to form a film, the PE film is used for an outer-layer composite film of a vacuum heat-insulating plate, and the outer-layer composite film sequentially comprises a PE film, a polyamide film, an aluminum foil, a PET film and glass fiber cloth from inside to outside; the vacuum insulation panel outer composite film prepared by taking the PE film as the innermost layer achieves the A-level fire-proof level, and has good heat-insulating property and strong puncture resistance.

Description

PE film and outer composite film with puncture resistance and flame retardance for vacuum insulation panel
Technical Field
The invention relates to the technical field of vacuum heat-insulating plates, in particular to a PE film and an outer layer composite film which are used for a vacuum heat-insulating plate and have puncture resistance and flame retardance.
Background
Environmental protection and energy conservation become the subject of economic development in the world at present, the development of efficient and energy-saving environment-friendly materials becomes an urgent need for relieving the energy crisis, and Vacuum Insulation panels (Vacuum Insulation panels) are in time and are widely applied to the fields of refrigerators, refrigerated containers, buildings and the like at present. VIP is a vacuum heat insulation material prepared based on a vacuum heat insulation mechanism, mainly comprises three parts, namely a vacuumized core layer porous medium heat insulation material, a gas insulation structure for isolating a core material from the outside and a gas adsorption material, and realizes heat insulation by improving the vacuum degree of the core material to the maximum extent. However, how to ensure the thermal stability and long-term effectiveness of VIP throughout the system life has become a major concern for many researchers and users.
In fact, the thermal conductivity of VIP is not constant, and as the VIP is used in a thermal insulation environment for a long time, external air permeates into the VIP through the air-barrier structure, so that the thermal insulation performance of the VIP is reduced, and the thermal conductivity of the VIP is increased. I.e., the increase in VIP thermal conductivity, is primarily due to gas permeation and moisture uptake by the core material. At present, most of the gas barrier structural films are formed by compounding several materials, and generally comprise a gas barrier layer, a heat barrier layer, a radiation protection layer, a heat seal layer and the like, and at least comprise the gas barrier layer and the heat seal layer. The most commonly used high-barrier composite film at present mostly comprises an aluminum foil as a gas barrier layer, low-density polyethylene as a heat seal layer and polyethylene terephthalate as a supporting and heat-blocking material.
The air barrier structure is an important component of the VIP plate and mainly plays a role in forming a certain closed space, blocking the permeation of external air and water vapor and maintaining the internal vacuum degree of the core material so as to maintain the heat insulation performance of the VIP, so that the air barrier performance of the air barrier structure is the most important factor influencing the internal vacuum degree and the service life of the VIP. In addition, because the air-barrier structural film is arranged between the inner core material of the VIP panel and the external environment (working condition), the air-barrier structural film also has certain requirements on puncture resistance so as to prolong the service life of the air-barrier structural film.
Disclosure of Invention
The invention aims to provide a PE film and an outer layer composite film for a vacuum insulation panel, wherein the PE film has puncture resistance and flame retardant performance, has high flame retardant, gas barrier and waterproof performance and simultaneously has excellent puncture resistance. The vacuum insulation panel outer composite film prepared by taking the PE film as the innermost layer reaches the A-level fireproof grade, and has good heat insulation performance and strong puncture resistance.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the PE film with puncture resistance and flame retardance for the vacuum heat-insulating plate comprises the following preparation raw materials of flame-retardant master batches, linear polyethylene (7042), high-pressure polyethylene (HDPE) and a brominated flame retardant, wherein: the PE film comprises the following raw materials in percentage by weight:
Figure BDA0002923744600000021
the flame-retardant master batch is obtained by mixing linear low-density polyethylene (7042), POE plastic and superfine magnesium hydroxide powder, and then mixing by an internal mixer and extruding and granulating; the flame-retardant master batch comprises the following components in percentage by weight:
linear low density polyethylene (7042) 30-45%;
10-15% of POE plastic;
40-60% of superfine magnesium hydroxide powder.
The median diameter (D50) of the superfine magnesium hydroxide powder is 1-10 μm; conventional antioxidant and lubricant can be added during the preparation of the flame-retardant master batch, and the addition amount of the antioxidant is 0.2-0.5 wt.%; the lubricant is added in an amount of 0.2-0.5 wt.%. The bromine content in the brominated flame retardant is more than 75 wt.%.
In the preparation process of the flame-retardant master batch, the banburying temperature of an internal mixer is about 170 ℃, and the temperature of each section of an extruder is 150-190 ℃. The specific temperature can be adjusted according to the actual situation during production.
The preparation process of the PE film with puncture resistance and flame retardance comprises the following steps: and mixing the flame-retardant master batches, the linear polyethylene, the high-pressure polyethylene (HDPE) and the brominated flame retardant in proportion, and extruding and blowing the mixture at the film blowing temperature of 170-185 ℃ to obtain the glass fiber cloth.
The thickness of the PE film is 8-15C.
The flame-retardant master batch is dried before use at the temperature of 90-105 ℃ for 6-8 hours.
The PE film is used for the innermost layer of the outer composite film of the vacuum insulation panel. The outer-layer composite film of the vacuum heat-insulating plate is of a five-layer composite structure and sequentially comprises a PE film, a polyamide film (PA), an aluminum foil, a PET film and medium-alkali glass fiber cloth from inside to outside; wherein: the thickness of the PE film is 8-15C, the thickness of the polyamide film is 1.2-1.7C, the thickness of the aluminum foil is 0.5-1.0C, the thickness of the PET film is 1.0-1.5C, and the content of the medium-alkali glass fiber cloth is 120g/m2And (4) arranging.
The pH value of the medium-alkali glass fiber cloth is 7-10.
The design principle and the beneficial effects of the invention are as follows:
1. the improved PE film is used as the innermost film of the outer composite film of the vacuum heat-insulating plate, and the outer composite film of the vacuum heat-insulating plate reaches the A-level fireproof grade through determination, and has strong puncture resistance (the puncture resistance strength is more than or equal to 12N).
2. When the PE film is prepared, the flame-retardant master batch is dried at the temperature of 90-105 ℃ for 6-8 hours. When the temperature is lower than 90 ℃, bubbles are easy to appear when the flame-retardant master batches are mixed with LLDPE and blown into the film, and when the temperature is higher than 105 ℃, the flame-retardant master batches are stuck together when being dried, thereby affecting the uniformity of the subsequent blown film.
3. The flame-retardant master batch designed by the invention takes superfine magnesium hydroxide powder as a flame retardant, namely, the flame-retardant master batch has flame retardant property, and can absorb part of combustion heat value under the high-temperature condition, thereby further improving the heat insulation property of the prepared vacuum heat-insulating plate outer layer composite film.
4. The flame-retardant master batch designed by the invention adopts an inorganic flame retardant, and the PE film prepared by mixing the inorganic flame retardant with other components in a certain ratio has the performances of ageing resistance, shrinkage reduction and the like.
Drawings
FIG. 1 is a schematic structural diagram of an outer composite film of a vacuum insulation panel.
Detailed Description
For a further understanding of the present invention, the following description is given in conjunction with the examples which are set forth to illustrate, but are not to be construed to limit the present invention, features and advantages.
Example 1
This example is a preparation of PE film, and the specific process is as follows:
1. preparing a flame-retardant master batch: the flame-retardant master batch is prepared by mixing linear low-density polyethylene (7042), POE plastic and superfine magnesium hydroxide powder, mixing by an internal mixer at 170 ℃, extruding and granulating, wherein the temperature of each section of the extruder is 150-190 ℃; the flame-retardant master batch comprises the following components in percentage by weight: 37.5 percent of linear low density polyethylene (7042), 12.5 percent of POE plastic, 49.4 percent of superfine magnesium hydroxide powder, 0.3 percent of antioxidant 1010 and 0.3 percent of lubricant (TAS-2A). Wherein the median diameter (D50) of the superfine magnesium hydroxide powder is 3-8 μm.
2. And drying the prepared flame-retardant master batch at the temperature of 100 ℃ for 7.5 hours. The drying temperature is based on the fact that after mixing with linear polyethylene 7042, the blown film has no bubbles, and if the temperature exceeds 110 ℃, the particles are stuck together.
3. Preparing a PE film: mixing the dried flame-retardant master batch, linear polyethylene 7042, high-pressure polyethylene (HDPE) and a bromine flame retardant, wherein the PE film comprises the following raw materials in percentage by weight: 58% of flame-retardant master batch, 18% of linear polyethylene (7042), 18% of high-pressure polyethylene (HDPE) and 6% of brominated flame retardant. The extrusion film blowing temperature is 180 ℃, and the temperature of each section can be adjusted according to the state of an extrusion pipe film due to different equipment. The bromine content in the brominated flame retardant is more than 75 wt.%.
Example 2
The embodiment is a preparation method of an outer layer composite film for a vacuum insulation panel, and the specific process is as follows:
the PE film prepared in example 1 is used as an innermost layer, and the PE film, the polyamide film, the aluminum foil, the PET film and the medium-alkali glass fiber cloth are sequentially arranged from inside to outside (figure 1); wherein: the thickness of the PE film is 110 mu m, the thickness of the polyamide film is 1.5C, the thickness of the aluminum foil is 0.7C, the thickness of the PET film is 1.2C, and the content of the medium-alkali glass fiber cloth is 110g/m2And (4) arranging.
The performance test of the prepared outer composite membrane for the vacuum insulation panel is shown in table 1.
TABLE 1 Performance of outer layer composite film (fiberglass cloth 110g/PET12 μm/Al 7 μm/PA15 μm/PE110 μm)
Figure BDA0002923744600000041
Figure BDA0002923744600000051

Claims (10)

1. A PE film with puncture resistance and flame retardant property for a vacuum insulation panel is characterized in that: the preparation raw materials of the PE film comprise flame-retardant master batches, linear polyethylene (7042), high-pressure polyethylene (HDPE) and a brominated flame retardant, wherein: the PE film comprises the following raw materials in percentage by weight:
Figure FDA0002923744590000011
2. the PE film with puncture and flame retardant properties for vacuum insulation panels according to claim 1, wherein: the flame-retardant master batch is obtained by mixing linear low-density polyethylene (7042), POE plastic and superfine magnesium hydroxide powder, and then mixing by an internal mixer and extruding and granulating; the flame-retardant master batch comprises the following components in percentage by weight:
linear low density polyethylene (7042) 30-45%;
10-15% of POE plastic;
40-60% of superfine magnesium hydroxide powder.
3. The PE film with puncture and flame retardant properties for vacuum insulation panels according to claim 2, wherein: the median diameter (D50) of the superfine magnesium hydroxide powder is 1-10 μm; conventional antioxidant and lubricant can be added during the preparation of the flame-retardant master batch, and the addition amount of the antioxidant is 0.2-0.5 wt.%; the addition amount of the lubricant is 0.2-0.5 wt%.
4. The PE film with puncture and flame retardant properties for vacuum insulation panels according to claim 2, wherein: in the preparation process of the flame-retardant master batch, the banburying temperature of an internal mixer is about 170 ℃, and the temperature of each section of an extruder is 150-190 ℃. The specific temperature can be adjusted according to the actual situation during production.
5. The PE film with puncture and flame retardant properties for vacuum insulation panels according to claim 2, wherein: the preparation process of the PE film with puncture resistance and flame retardance comprises the following steps: and mixing the flame-retardant master batches, the linear polyethylene, the high-pressure polyethylene (HDPE) and the brominated flame retardant in proportion, and extruding and blowing the mixture at the film blowing temperature of 170-185 ℃ to obtain the glass fiber cloth.
6. The PE film with puncture and flame retardant properties for vacuum insulation panels according to claim 5, wherein: the thickness of the PE film is 8-15C.
7. The PE film with puncture and flame retardant properties for vacuum insulation panels according to claim 5, wherein: the flame-retardant master batch is dried before use at the temperature of 90-105 ℃ for 6-8 hours.
8. An outer composite film for a vacuum insulation panel comprising the PE film according to any one of claims 1 to 7, wherein: the PE film is used for the innermost layer of the outer composite film of the vacuum insulation panel.
9. An exterior composite film for a vacuum insulation panel according to claim 8 wherein: the outer-layer composite film of the vacuum heat-insulating plate is of a five-layer composite structure and sequentially comprises a PE film, a polyamide film (PA), an aluminum foil, a PET film and medium-alkali glass fiber cloth from inside to outside; wherein: the thickness of the PE film is 8-15C, the thickness of the polyamide film is 1.2-1.7C, the thickness of the aluminum foil is 0.5-1.0C, the thickness of the PET film is 1.0-1.5C, and the content of the medium-alkali glass fiber cloth is 120g/m2And (4) arranging.
10. An exterior composite film for a vacuum insulation panel according to claim 9 wherein: the pH value of the medium-alkali glass fiber cloth is 7-10.
CN202110125203.3A 2021-01-29 2021-01-29 PE film and outer composite film with puncture resistance and flame retardance for vacuum insulation panel Pending CN112898673A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN207808664U (en) * 2017-08-14 2018-09-04 惠州市道科包装材料有限公司 A kind of low-cost flame-retardant film of STP
CN110228253A (en) * 2019-06-12 2019-09-13 江苏凯伦建材股份有限公司 A kind of high barrier sheet and preparation method thereof of fire-retardant puncture resistant

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN207808664U (en) * 2017-08-14 2018-09-04 惠州市道科包装材料有限公司 A kind of low-cost flame-retardant film of STP
CN110228253A (en) * 2019-06-12 2019-09-13 江苏凯伦建材股份有限公司 A kind of high barrier sheet and preparation method thereof of fire-retardant puncture resistant

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
中华人民共和国公安部消防局编: "中国消防手册 第十二卷 消防装备 消防产品", vol. 1, 上海科学技术文献出版社, pages: 124 *

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