CN116199602A - Preparation process and application of high-temperature environment-friendly foaming agent barium azodicarbonate - Google Patents
Preparation process and application of high-temperature environment-friendly foaming agent barium azodicarbonate Download PDFInfo
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- CN116199602A CN116199602A CN202310216801.0A CN202310216801A CN116199602A CN 116199602 A CN116199602 A CN 116199602A CN 202310216801 A CN202310216801 A CN 202310216801A CN 116199602 A CN116199602 A CN 116199602A
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- 229910052788 barium Inorganic materials 0.000 title claims abstract description 39
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000004088 foaming agent Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000005187 foaming Methods 0.000 claims abstract description 27
- 239000004156 Azodicarbonamide Substances 0.000 claims abstract description 16
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims abstract description 16
- 235000019399 azodicarbonamide Nutrition 0.000 claims abstract description 16
- 239000004677 Nylon Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 229920001778 nylon Polymers 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 229920000728 polyester Polymers 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims abstract description 4
- 229910001863 barium hydroxide Inorganic materials 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 18
- 239000002131 composite material Substances 0.000 claims description 16
- 229920001169 thermoplastic Polymers 0.000 claims description 11
- 239000004416 thermosoftening plastic Substances 0.000 claims description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000001746 injection moulding Methods 0.000 claims description 8
- 235000021355 Stearic acid Nutrition 0.000 claims description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 6
- 239000008117 stearic acid Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 abstract description 11
- 229920006351 engineering plastic Polymers 0.000 abstract description 9
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 abstract description 6
- 239000004033 plastic Substances 0.000 abstract description 6
- 229920003023 plastic Polymers 0.000 abstract description 6
- 238000000354 decomposition reaction Methods 0.000 abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 21
- 239000000126 substance Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 4
- 239000004604 Blowing Agent Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000013585 weight reducing agent Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 210000000497 foam cell Anatomy 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000011667 zinc carbonate Substances 0.000 description 2
- 235000004416 zinc carbonate Nutrition 0.000 description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 description 2
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- ONIOAEVPMYCHKX-UHFFFAOYSA-N carbonic acid;zinc Chemical compound [Zn].OC(O)=O ONIOAEVPMYCHKX-UHFFFAOYSA-N 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C281/00—Derivatives of carbonic acid containing functional groups covered by groups C07C269/00 - C07C279/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group
- C07C281/20—Derivatives of carbonic acid containing functional groups covered by groups C07C269/00 - C07C279/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group the two nitrogen atoms of the functional groups being doubly-bound to each other, e.g. azoformamide
-
- 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
-
- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; 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
- 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
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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
- 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
- C08J2423/08—Copolymers of ethene
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention belongs to the technical field of foaming agents, and particularly relates to a preparation process of a high-temperature environment-friendly (decomposition product is free of ammonia gas and formamide) foaming agent barium azodicarbonate and application of the foaming agent barium azodicarbonate in engineering plastics. The preparation process comprises the following steps: s1: taking azodicarbonamide and barium hydroxide as raw materials, taking water as a solvent, and catalyzing by inorganic strong alkali to hydrolyze the azodicarbonamide and then directly salify; s2: after the reaction in the step S1 is finished, the generated barium azodicarbonate is separated out and is deposited in an aqueous solution, and then the barium azodicarbonate is separated out by filtration; s3: and drying the separated barium azodicarbonate to obtain the target product. The process has the advantages of one-step synthesis, water as solvent, safety, environmental protection, high yield, simple operation and convenient and easily obtained raw materials. The barium azodicarbonate can be suitable for foaming nylon compounds (PA 6, PA66, PA610, PA612 and the like) and polyester compounds (PET, PBT and the like), and can be expanded into other high-performance plastic foaming materials processed at high temperature.
Description
Technical Field
The invention belongs to the technical field of foaming agents, and particularly relates to a preparation process of a high-temperature environment-friendly (decomposition product is free of ammonia gas and formamide) foaming agent barium azodicarbonate and application of the foaming agent barium azodicarbonate in engineering plastics.
Background
Blowing agents refer to a class of additives that are capable of forming a cellular structure in a plastic, i.e., to be added to make a foam. They can generate a large amount of gas under specific conditions, and the formed porous structure material containing continuous or discontinuous air holes (i.e. open holes or closed holes) and making the plastic form gas-solid phase combination can reduce the density and hardness of the plastic or enhance the sound insulation and heat insulation of the plastic.
The chemical foaming agents commonly used in the market at present are mainly divided into exothermic foaming agents and endothermic foaming agents.
Exothermic blowing agents are mainly of the three main classes azo, nitroso and sulfonyl hydrazides, however none of these blowing agents have a rise temperature of more than 250 ℃. Among them, azodicarbonamide (ADC) foaming agents, which are most widely used, have a starting temperature of 190-210 ℃ and have a large gas generation amount, but decomposition products have toxic substances such as ammonia, formamide, etc., so that the non-environmental protection is a fatal weakness.
For the foaming agent of heat-absorbing baking soda and citric acid, although the environment-friendly nontoxic harmful gas is generated, the gas generation amount is smaller, and the decomposition product is mainly carbon dioxide, but the initiation temperature is lower.
For foaming of engineering plastics with high melting point (melting point greater than 220 ℃) it is necessary to select a chemical foaming agent with a high foaming temperature (preferably a foaming temperature above 250 ℃) so that the foaming process can be matched with the melt processing process of the engineering plastics. Therefore, the two common exothermic and endothermic chemical foaming agents are not suitable for foaming high-melting-point high polymer materials such as engineering plastic foaming and the like, and the chemical foaming agents are limited to be applied to high ends such as automobile weight reduction, aerospace weight reduction, engineering plastic modification, special military industry and the like.
Disclosure of Invention
The invention aims to provide a preparation process and application of a high-temperature environment-friendly (decomposition product is ammonia-free and formamide-free) foaming agent barium azodicarbonate, so as to solve the problems in the prior art.
In order to achieve the above purpose, the present invention provides the following technical solutions:
in one aspect, a preparation process of a high-temperature environment-friendly foaming agent barium azodicarbonate is provided, which comprises the following steps:
s1: taking azodicarbonamide and barium hydroxide as raw materials, taking water as a solvent, and catalyzing by inorganic strong alkali to hydrolyze the azodicarbonamide and then directly salify;
s2: after the reaction in the step S1 is finished, the generated barium azodicarbonate is separated out and is deposited in an aqueous solution, and then the barium azodicarbonate is separated out by filtration;
s3: drying the separated barium azodicarbonate to obtain a target product;
the chemical reaction equation in step S1 is:
in the above embodiment, in step S1, after azodicarbonamide is left at 0.5% or less, the reaction is completed.
The reaction temperature in the step s1 is-10 ℃ to 20 ℃.
The drying temperature in the step S3 is 10-70 ℃.
The inorganic strong base in the step S1 is one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide.
In a second aspect, a foamed nylon composite composition is provided, comprising the following components in percentage by weight:
in a third aspect, there is also provided a foamable thermoplastic polyester composite composition consisting of the following components in weight percent:
in a fourth aspect, there is provided a method for preparing the foamable composition described above, the foamable composition being foamed by injection molding, wherein secondary opening is required for foaming, and the secondary opening is at a distance of 1.0 to 2.0mm.
Additional aspects and advantages of the invention will be described in detail in connection with the examples to make the effects apparent.
Drawings
FIG. 1 is an infrared spectrum of barium azodicarbonate;
FIG. 2 is a thermogram of barium azodicarbonate;
Detailed Description
Technical solutions in the embodiments of the present application will be clearly described below with reference to the drawings in the embodiments of the present application, and it is apparent that the described embodiments are some of the embodiments of the present application, but not all of the embodiments. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments in the present application are within the scope of the protection of the present application.
In the description of the present application, it is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments in accordance with the present application. For ease of description, the dimensions of the various features shown in the drawings are not drawn to actual scale. Techniques, methods, and apparatus known to one of ordinary skill in the relevant art may not be discussed in detail, but should be considered part of the specification where appropriate. In all examples shown and discussed herein, any specific values should be construed as merely illustrative, and not a limitation. Thus, other examples of the exemplary embodiments may have different values. It should be noted that: like reference numerals and letters denote like items in the following figures, and thus once an item is defined in one figure, no further discussion thereof is necessary in subsequent figures.
As shown in figures 1 and 2, regarding the high-temperature foaming agent barium azodicarbonate, the foaming temperature is high, the initiation temperature is 250 ℃, the termination gas generation temperature is 300 ℃, the gas generation amount is 60ml-90ml/g (the document reports that the gas generation amount is 170-175ml/g which is a theoretical calculated value and is not a truly measured value), compared with the general exothermic chemical foaming agent barium azodicarbonate (190-210 ℃), the high-temperature foaming agent barium azodicarbonate has the advantages of no toxic gas as a degradation product, environmental protection, mild and controllable gas generation process and high initiation temperature, thereby widening the application of the high-temperature foaming agent barium azodicarbonate in foaming engineering plastics with high melting points.
Example 1:
the embodiment provides a synthesis method of barium azodicarbonate, which is characterized by one-step synthesis, water as solvent, safety, environmental protection, high yield, simple operation and convenient and easily obtained raw materials. The method comprises the following steps:
s1: taking azodicarbonamide and barium hydroxide as raw materials, taking water as a solvent, and catalyzing by inorganic strong alkali to hydrolyze the azodicarbonamide and then directly salify;
s2: after the reaction in the step S1 is finished, the generated barium azodicarbonate is separated out and is deposited in an aqueous solution, and then the barium azodicarbonate is separated out by filtration;
s3: drying the separated barium azodicarbonate to obtain a target product;
the chemical reaction equation in step S1 is:
preferably, in step S1, after azodicarbonamide remains to 0.5% or less, the reaction is completed.
The reaction temperature in the step s1 is-10 ℃ to 20 ℃.
The drying temperature in the step S3 is 10-70 ℃.
The inorganic strong base in the step S1 is one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide.
Example 2:
the applicant researches the feasibility of foaming the high-temperature environment-friendly chemical foaming agent barium azodicarbonate in a thermoplastic nylon compound, and particularly relates to a foaming nylon compound composition which comprises the following components in percentage by weight:
other processing aids are stearic acid, stearic acid complex esters, and the like.
The foaming nylon compound composition is foamed by injection molding, wherein secondary mold opening is needed during foaming, and the distance of the secondary mold opening is 1.0-2.0mm. The secondary mold opening refers to: after the whole cavity is filled with the compound melt through an extruder, the compound melt is opened slightly in the thickness direction or the variable cavity core is retracted, the primary mold opening is carried out, the quick release of pressure is realized, a large number of cells are induced to be generated simultaneously, then the secondary mold opening is carried out, and the molded resin matrix is taken out.
Regarding the production of the foamed nylon composite composition, the following test was conducted,
test one:
the above numbers 1-2 are control groups without adding barium azodicarbonate, the number 3 is a test group without secondary mold opening, after injection molding, the densities of the resin matrixes in the numbers 1 and 2 are similar, no obvious change occurs, the main reason is that no foaming agent is added, no foam cells are generated in the resin matrixes, the resin matrix in the test 3 starts to change, foam cells are generated in the resin matrixes, and compared with the numbers 1 and 2, the density is reduced, and the weight reduction of 7.0% is achieved under the same volume.
After several tests, it was found that the density of the injection molded resin matrix was not only related to the material being produced, but also related to the injection molding method, and for this purpose, tests No. 4-7 were carried out, and the test No. 4-7 was based on the raw material, and the demolding process of the injection molded product was adjusted, specifically, a secondary demolding, i.e., a secondary mold opening, was employed, and after controlling the distance of the mold opening, it was found that a foamed nylon resin matrix having a lighter weight and more uniform cells could be obtained by the secondary mold opening. However, it should be noted that the secondary mold opening distance cannot be too large, otherwise large bulge is caused, and under the control of the number 4-7, the secondary mold opening distance is controlled to be 1.3mm, so that the appearance is ensured, and the weight is reduced by 25.3%.
And (2) testing II:
the second test is a control test, the traditional azodicarbonamide is adopted for foaming, and the foaming behavior of the azodicarbonamide is not as good as that of the barium azodicarbonate after the control of the first test and the second test.
And (3) test III:
test three is a control test, adopting a heat-absorbing high-temperature foaming agent PS516KS (brand name of Jie New Material Co., ltd.) and a foaming behavior test of a heat-absorbing foaming agent ZnCO3 in a PA nylon compound,
the test results show that the whole foaming process is uncontrollable, the foam holes are larger and have broken holes, and the high-temperature heat-absorbing foaming agent is not suitable for the combination.
The applicant has also studied the feasibility of foaming the high-temperature environment-friendly chemical foaming agent barium azodicarbonate in a thermoplastic polyester composite, in particular to a foamable thermoplastic polyester composite composition which comprises the following components in percentage by weight:
the foaming thermoplastic polyester compound composition is foamed by injection molding, wherein secondary mold opening is needed during foaming, and the distance of the secondary mold opening is 1.0-2.0mm.
Regarding the production of the foamed thermoplastic polyester composite composition, the following test, test four, was performed:
the above-mentioned reference number 1 is a control group to which no barium azodicarbonate was added, and the reference numbers 2 to 3 are test groups, and it was found from the above-mentioned test that adding barium azodicarbonate can reduce weight by 15% while securing appearance after injection molding.
According to the experimental results of the above experiments 1-4, the high-temperature heat-release environment-friendly chemical foaming agent barium azodicarbonate can be uniformly foamed in specific engineering plastic composites (thermoplastic nylon PA, thermoplastic polyester PBT and the like), and the foaming effect in the specific engineering plastic composites is superior to that of the general heat-release chemical foaming agent azodicarbonamide AC, and is greatly superior to that of the general heat-absorption chemical foaming agent PS516KS and zinc carbonate. The foaming agent can be suitable for foaming nylon compounds (PA 6, PA66, PA610, PA612 and the like) and polyester compounds (PET, PBT and the like), and can be also expanded into other high-performance plastic foaming materials processed at high temperature.
The embodiments of the present application and the features of the embodiments may be combined without conflict, and the present application is not limited to the specific embodiments described above, which are merely illustrative, not restrictive, and many forms may be made by those of ordinary skill in the art, without departing from the spirit of the present application and the scope of the claims, which are also within the protection of the present application.
Claims (10)
1. The preparation process of the high-temperature foaming agent barium azodicarbonate is characterized by comprising the following steps of:
s1: taking azodicarbonamide and barium hydroxide as raw materials, taking water as a solvent, and catalyzing by inorganic strong alkali to hydrolyze the azodicarbonamide and then directly salify;
s2: after the reaction in the step S1 is finished, the generated barium azodicarbonate is separated out and is deposited in an aqueous solution, and then the barium azodicarbonate is separated out by filtration;
s3: drying the separated barium azodicarbonate to obtain a target product;
the chemical reaction equation in step S1 is:
2. the process for preparing barium azodicarbonate as claimed in claim 1, wherein in step S1, after the azodicarbonamide is left to be 0.5% or less, the reaction is completed; the reaction temperature in the step s1 is-10 ℃ to 20 ℃.
3. The process for preparing barium azodicarbonate as claimed in claim 1, wherein the drying temperature in step S3 is 10-70 ℃.
4. The process for preparing the high-temperature foaming agent barium azodicarbonate according to claim 1, wherein the inorganic strong base in the step S1 is one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide.
5. A foamable nylon composite composition, which is characterized by comprising the following components in percentage by weight:
6. a foamable nylon composite composition according to claim 5, wherein the other processing aid is stearic acid, a stearic acid complex ester or the like.
7. A process for the preparation of a foamable nylon composite composition according to claim 5 or 6, wherein the foamable composite composition is foamed by injection molding, wherein secondary mold opening is required for foaming, and the secondary mold opening is at a distance of 1.0 to 2.0mm.
8. A foamable thermoplastic polyester composite composition, characterized by comprising the following components in weight percent:
9. a foamable thermoplastic polyester composite composition according to claim 8, wherein the other processing aid is stearic acid, a stearic acid complex ester or the like.
10. A process for the preparation of a foamable thermoplastic polyester composite composition according to claim 8 or 9, wherein the foamable composite composition is foamed by injection moulding, wherein secondary mould opening is required for foaming and the secondary mould opening is at a distance of 1.0-2.0mm.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU170067A1 (en) * | Г. М. Стронгин , Я. Ю. Рекшинский | |||
| GB1007988A (en) * | 1961-09-13 | 1965-10-22 | Nat Distillers Chem Corp | Molded plastic foams |
| CN103415558A (en) * | 2011-03-09 | 2013-11-27 | 东丽株式会社 | Crosslinked polyolefin resin foam |
| CN112469773A (en) * | 2018-07-27 | 2021-03-09 | 株式会社大阪曹达 | Composition for sound absorbing material |
| CN115286841A (en) * | 2022-08-24 | 2022-11-04 | 宁波公牛电器有限公司 | Metal powder compound and preparation method thereof, spraying-free PC (polycarbonate) composite material and preparation method thereof, and metal-texture injection molding part |
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2023
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU170067A1 (en) * | Г. М. Стронгин , Я. Ю. Рекшинский | |||
| GB1007988A (en) * | 1961-09-13 | 1965-10-22 | Nat Distillers Chem Corp | Molded plastic foams |
| CN103415558A (en) * | 2011-03-09 | 2013-11-27 | 东丽株式会社 | Crosslinked polyolefin resin foam |
| CN112469773A (en) * | 2018-07-27 | 2021-03-09 | 株式会社大阪曹达 | Composition for sound absorbing material |
| CN115286841A (en) * | 2022-08-24 | 2022-11-04 | 宁波公牛电器有限公司 | Metal powder compound and preparation method thereof, spraying-free PC (polycarbonate) composite material and preparation method thereof, and metal-texture injection molding part |
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