CN110540725A - degradable halogen-free flame-retardant foaming material and preparation method thereof - Google Patents
degradable halogen-free flame-retardant foaming material and preparation method thereof Download PDFInfo
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- CN110540725A CN110540725A CN201810543413.2A CN201810543413A CN110540725A CN 110540725 A CN110540725 A CN 110540725A CN 201810543413 A CN201810543413 A CN 201810543413A CN 110540725 A CN110540725 A CN 110540725A
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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
- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
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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
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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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
- C08J9/0066—Use of inorganic compounding ingredients
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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
- C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
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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
- C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
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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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/22—Expandable microspheres, e.g. Expancel®
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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
- C08J2329/00—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 alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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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
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
Abstract
the invention provides a degradable halogen-free flame-retardant foam material and a preparation method thereof, wherein the degradable halogen-free flame-retardant foam material is prepared from the following raw materials in parts by mass: 45-70 parts of PVA, 5-15 parts of poly-beta-hydroxybutyric acid, 3-5 parts of glycerol, 20-30 parts of aluminum hydroxide, 3-5 parts of boehmite, 3-5 parts of foaming agent, 1-3 parts of cross-linking agent and 0.5 part of heat stabilizer through mixing and extrusion. The degradable halogen-free flame-retardant foaming material provided by the invention selects PVA with lower molecular weight and viscosity as a base material, and adds high-efficiency micromolecule plasticizer glycerol into the PVA matrix, so that the processing window of the foaming material is greatly expanded. While allowing the final material to achieve partially degradable and flame retardant properties.
Description
Technical Field
The invention relates to the field of general plastics, in particular to a degradable halogen-free flame-retardant foaming material and a preparation method thereof.
background
The polymer foam material is a foam material taking a polymer material as a matrix, and is widely applied to the packaging and transportation industry, the automobile industry and the building industry due to good performance and stability. However, since the material itself contains a large amount of bubbles, the combustion speed after exposure to open flame is extremely high, and therefore, flame retardant modification of the foam material used in special industries is required. The existing flame retardant added into the foaming material is usually a flame retardant product of a bromine-antimony system, and a large amount of toxic gas can be released in the combustion process to harm the life safety of human beings, so that the use of a flame retardant system which is more environment-friendly is an urgent need at present.
with the rapid development of the electronic commerce industry, the polymer foam material belongs to the packaging industry in the field of the most extensive application at present, but the environmental pollution caused by a large amount of disposable packaging materials is followed. How to rapidly recycle the product is also a big problem faced by the current high polymer foam material.
Disclosure of Invention
The invention aims to provide a degradable halogen-free flame-retardant foaming material and a preparation method thereof.
The technical scheme of the invention is as follows:
The degradable halogen-free flame-retardant foaming material is prepared from the following raw material components in percentage by mass:
in a further scheme, the PVA is powder with the intrinsic viscosity of 4.0-7.0 dl/g.
The foaming agent is a commercial microsphere foaming agent, and the foaming temperature of the foaming agent is 150 ℃.
The cross-linking agent is boric acid powder.
the heat stabilizer is at least three of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (1010), beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl ester (1076), tri- (2, 4-di-tert-butylphenyl) phosphite (168) and thiodipropionic acid dioctadecyl ester (DSTDP).
The invention also aims to provide a preparation method of the degradable halogen-free flame-retardant foaming material, which comprises the following steps:
Adding 45-70 parts of PVA, 5-10 parts of poly-beta-hydroxybutyric acid, 3-5 parts of glycerol, 20-30 parts of aluminum hydroxide, 3-5 parts of boehmite, 3-5 parts of foaming agent, 1-3 parts of cross-linking agent and 0.5 part of heat stabilizer into a high-speed mixer, mixing at low speed for 3min, adding the uniformly mixed materials into a double-screw plate extruder, mixing, extruding and cooling to obtain a final product; wherein the extrusion temperature of each extrusion zone in the twin-screw extruder is 160-.
Compared with the prior art, the invention has the following advantages:
The degradable halogen-free flame-retardant foaming material provided by the invention selects PVA with lower molecular weight and viscosity as a base material, and adds high-efficiency micromolecule plasticizer glycerol into the PVA matrix, so that the processing window of the foaming material is greatly expanded.
In addition, poly-beta-hydroxybutyrate (PHB) is a high molecular compound which can be completely decomposed by the nature, and has good biocompatibility. Degradable poly-beta-hydroxybutyrate (PHB) material is added in the invention, so that the final material can obtain partially degradable performance; and secondly, the addition of aluminum hydroxide and boehmite enables the material to have certain flame retardant property, the aluminum hydroxide plays a main flame retardant effect, and the boehmite serves as an auxiliary flame retardant.
Detailed Description
The invention is further described below with reference to specific embodiments (but not limited to the embodiments listed):
In the following examples, PVA is a powder with an intrinsic viscosity of 4.0-7.0dl/g, and the crosslinking agent is boric acid powder;
The heat stabilizer is at least three of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (1010), beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl ester (1076), tri- (2, 4-di-tert-butylphenyl) phosphite (168) and thiodipropionic acid dioctadecyl ester (DSTDP).
Example 1
Adding 70 parts of PVA, 10 parts of poly-beta-hydroxybutyric acid, 5 parts of glycerol, 20 parts of aluminum hydroxide, 5 parts of boehmite, 5 parts of foaming agent, 3 parts of cross-linking agent and 0.5 part of heat stabilizer into a high-speed mixer, mixing at low speed for 3min, adding the uniformly mixed materials into a double-screw plate extruder, mixing, extruding and cooling to obtain the final product. Wherein the extrusion temperatures of the extrusion intervals in the double-screw extruder are respectively 170 ℃, 180 ℃, 190 ℃ and 200 ℃. The product properties are shown in Table 1
Example 2
60 parts of PVA, 8 parts of poly-beta-hydroxybutyric acid, 4 parts of glycerol, 25 parts of aluminum hydroxide, 4 parts of boehmite, 4 parts of foaming agent, 2 parts of cross-linking agent and 0.5 part of heat stabilizer are added into a high-speed mixer, mixed for 3min at low speed, and then the uniformly mixed materials are added into a double-screw plate extruder to be subjected to mixing, extrusion and cooling to obtain the final product. Wherein the extrusion temperatures of the extrusion zones in the twin-screw extruder are 165 ℃, 175 ℃, 185 ℃ and 195 ℃ respectively. The product properties are shown in Table 1
Example 3
45 parts of PVA, 5 parts of poly-beta-hydroxybutyric acid, 3 parts of glycerol, 30 parts of aluminum hydroxide, 3 parts of boehmite, 3 parts of foaming agent, 1 part of cross-linking agent and 0.5 part of heat stabilizer are added into a high-speed mixer, mixed for 3min at low speed, and then the uniformly mixed materials are added into a double-screw plate extruder to be subjected to mixing, extrusion and cooling to obtain the final product. Wherein the extrusion temperatures of the extrusion intervals in the double-screw extruder are respectively 160 ℃, 170 ℃, 180 ℃ and 190 ℃. The product properties are shown in Table 1
TABLE 1
Comparative example 1
Adding 70 parts of PVA, 10 parts of poly-beta-hydroxybutyric acid, 5 parts of glycerol, 20 parts of aluminum hydroxide, 5 parts of foaming agent, 3 parts of cross-linking agent and 0.5 part of heat stabilizer into a high-speed mixer, mixing at low speed for 3min, adding the uniformly mixed materials into a double-screw plate extruder, mixing and extruding, and cooling to obtain the final product. Wherein the extrusion temperatures of the extrusion intervals in the double-screw extruder are respectively 170 ℃, 180 ℃, 190 ℃ and 200 ℃. The product properties are shown in Table 2
Comparative example 2
Adding 70 parts of PVA, 5 parts of glycerol, 20 parts of aluminum hydroxide, 5 parts of boehmite, 5 parts of a foaming agent, 3 parts of a cross-linking agent and 0.5 part of a heat stabilizer into a high-speed mixer, mixing for 3min at a low speed, adding the uniformly mixed materials into a double-screw plate extruder, mixing, extruding and cooling to obtain the final product. Wherein the extrusion temperatures of the extrusion intervals in the double-screw extruder are respectively 170 ℃, 180 ℃, 190 ℃ and 200 ℃. The product properties are shown in Table 2
Comparative example 3
Adding 70 parts of PVA, 10 parts of poly-beta-hydroxybutyric acid, 5 parts of glycerol, 20 parts of aluminum hydroxide, 5 parts of boehmite, 3 parts of a cross-linking agent and 0.5 part of a heat stabilizer into a high-speed mixer, mixing at a low speed for 3min, adding the uniformly mixed materials into a double-screw plate extruder, mixing and extruding, and cooling to obtain the final product. Wherein the extrusion temperatures of the extrusion intervals in the double-screw extruder are respectively 170 ℃, 180 ℃, 190 ℃ and 200 ℃. The product properties are shown in Table 2
TABLE 2
As can be seen from example 3 and comparative examples 1-3, the material prepared by the invention has good flame retardant and degradation properties, aluminum hydroxide plays a main flame retardant role, and boehmite serves as an auxiliary flame retardant; in addition, poly-beta-hydroxybutyrate plays an important role in the degradability of the material.
The embodiments described above are intended to facilitate one of ordinary skill in the art in understanding and using the present invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the embodiments described herein, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (6)
1. A degradable halogen-free flame-retardant foaming material is characterized in that: the composition is prepared from the following raw materials in parts by mass:
45-70 parts of PVA
5-15 parts of poly-beta-hydroxybutyric acid
3-5 parts of glycerol
20-30 parts of aluminum hydroxide
3-5 parts of boehmite
3-5 parts of foaming agent
1-3 parts of cross-linking agent
0.5 part of heat stabilizer.
2. The degradable halogen-free flame retardant foaming material of claim 1, wherein: the PVA is powder with intrinsic viscosity of 4.0-7.0 dl/g.
3. The degradable halogen-free flame retardant foaming material of claim 1, wherein: the foaming agent is a microsphere foaming agent, and the foaming temperature is 150 ℃.
4. the degradable halogen-free flame retardant foaming material of claim 1, wherein: the cross-linking agent is boric acid powder.
5. The degradable halogen-free flame retardant foaming material of claim 1, wherein: the heat stabilizer is at least three of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (1010), beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl ester (1076), tri- (2, 4-di-tert-butylphenyl) phosphite (168) and thiodipropionic acid dioctadecyl ester (DSTDP).
6. The preparation method of the degradable halogen-free flame retardant foaming material of claim 1, wherein the preparation method comprises the following steps: the method comprises the following steps: adding 45-70 parts of PVA, 5-10 parts of poly-beta-hydroxybutyric acid, 3-5 parts of glycerol, 20-30 parts of aluminum hydroxide, 3-5 parts of boehmite, 3-5 parts of foaming agent, 1-3 parts of cross-linking agent and 0.5 part of heat stabilizer into a high-speed mixer for mixing; then adding the uniformly mixed materials into a double-screw plate extruder, mixing, extruding and cooling to obtain a final product; wherein the extrusion temperature of each extrusion zone in the twin-screw extruder is 160-.
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| CN201810543413.2A CN110540725A (en) | 2018-05-29 | 2018-05-29 | degradable halogen-free flame-retardant foaming material and preparation method thereof |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1104656A (en) * | 1993-12-31 | 1995-07-05 | 中国科学院兰州化学物理研究所 | Biodegradable films and their production |
| CN1583851A (en) * | 2004-05-24 | 2005-02-23 | 华东理工大学 | Hydrophobic completely biological degradable materials and preparing method thereof |
| CN1939967A (en) * | 2005-09-30 | 2007-04-04 | 李小鲁 | Hydrophobic degradable biological material, its production and foaming products |
| CN102241862A (en) * | 2010-05-14 | 2011-11-16 | 北京化工大学 | Preparation of water resistant polyvinyl alcohol biodegradable film through melt extrusion method |
| CN102304260A (en) * | 2011-07-18 | 2012-01-04 | 北京工商大学 | Polyvinyl alcohol foaming material and manufacture method thereof |
| CN103579559A (en) * | 2012-07-30 | 2014-02-12 | 海洋王照明科技股份有限公司 | Diaphragm of electrochemical power supply and preparation method thereof |
| CN105968670A (en) * | 2016-05-26 | 2016-09-28 | 李谚华 | Flame-retardant polyvinyl alcohol foam material |
| CN107556675A (en) * | 2017-09-11 | 2018-01-09 | 浙江闪铸三维科技有限公司 | A kind of polyvinyl alcohol water solubility 3D printing support consumptive material and preparation method thereof |
-
2018
- 2018-05-29 CN CN201810543413.2A patent/CN110540725A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1104656A (en) * | 1993-12-31 | 1995-07-05 | 中国科学院兰州化学物理研究所 | Biodegradable films and their production |
| CN1583851A (en) * | 2004-05-24 | 2005-02-23 | 华东理工大学 | Hydrophobic completely biological degradable materials and preparing method thereof |
| CN1939967A (en) * | 2005-09-30 | 2007-04-04 | 李小鲁 | Hydrophobic degradable biological material, its production and foaming products |
| CN102241862A (en) * | 2010-05-14 | 2011-11-16 | 北京化工大学 | Preparation of water resistant polyvinyl alcohol biodegradable film through melt extrusion method |
| CN102304260A (en) * | 2011-07-18 | 2012-01-04 | 北京工商大学 | Polyvinyl alcohol foaming material and manufacture method thereof |
| CN103579559A (en) * | 2012-07-30 | 2014-02-12 | 海洋王照明科技股份有限公司 | Diaphragm of electrochemical power supply and preparation method thereof |
| CN105968670A (en) * | 2016-05-26 | 2016-09-28 | 李谚华 | Flame-retardant polyvinyl alcohol foam material |
| CN107556675A (en) * | 2017-09-11 | 2018-01-09 | 浙江闪铸三维科技有限公司 | A kind of polyvinyl alcohol water solubility 3D printing support consumptive material and preparation method thereof |
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