CN111534025A - Shape memory material and preparation method thereof - Google Patents
Shape memory material and preparation method thereof Download PDFInfo
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- CN111534025A CN111534025A CN202010458793.7A CN202010458793A CN111534025A CN 111534025 A CN111534025 A CN 111534025A CN 202010458793 A CN202010458793 A CN 202010458793A CN 111534025 A CN111534025 A CN 111534025A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions 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; Compositions of derivatives of such polymers
- C08L27/02—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- C—CHEMISTRY; METALLURGY
- 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
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- 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
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/12—Shape memory
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a shape memory material which comprises the following raw materials in parts by weight: 88-118 parts of PVC resin powder, 1-3 parts of trans-1, 4-polyisoprene rubber, 1-3 parts of acrylate rubber, 5-8 parts of poly (acrylonitrile-butadiene-styrene), 7-10 parts of dibutyl phthalate, 2-5 parts of tribasic lead sulfate, 1-3 parts of calcium stearate, 0.5-1.5 parts of nano zinc oxide, 3-5 parts of nano calcium carbonate, 2-4 parts of silicon nitride whisker, 1-3 parts of dicyclopentadiene potassium diformate and 0.5-1.5 parts of anti-aging agent. The trans-1, 4-polyisoprene rubber, the acrylate rubber and the poly (acrylonitrile-butadiene-styrene) are added, so that the material has a good shape memory function, the comprehensive performance of the material is improved by adding the nano zinc oxide, the nano calcium carbonate, the silicon nitride whisker and the like, and the service life of the material is prolonged by adding the anti-aging agent.
Description
Technical Field
The invention relates to the field of functional materials, in particular to a shape memory material and a preparation method thereof.
Background
The shape memory material is an important functional material, wherein the development of the high molecular polymer shape memory material is rapid in recent years, and compared with the traditional functional material, the polymer shape memory material has the advantages of large deformation amount, wide recovery range, easiness in processing, low energy consumption, low cost and the like, and has wide application prospect for materials such as cross-linked polyethylene, polystyrene, polyurethane, polylactic acid, polycaprolactone and the like with shape memory characteristics which are developed. However, the memory performance of the existing shape memory materials is not obvious.
Disclosure of Invention
One of the objects of the present invention is: provides a shape memory material with good memory effect.
In order to achieve the above purpose, the invention provides the following technical scheme:
a shape memory material comprises the following raw materials in parts by weight:
88-118 parts of PVC resin powder, 1-3 parts of trans-1, 4-polyisoprene rubber, 1-3 parts of acrylate rubber, 5-8 parts of poly (acrylonitrile-butadiene-styrene), 7-10 parts of dibutyl phthalate, 2-5 parts of tribasic lead sulfate, 1-3 parts of calcium stearate, 0.5-1.5 parts of nano zinc oxide, 3-5 parts of nano calcium carbonate, 2-4 parts of silicon nitride whisker, 1-3 parts of dicyclopentadiene potassium diformate and 0.5-1.5 parts of anti-aging agent.
Preferably, the shape memory material comprises the following raw materials in parts by weight:
100 parts of PVC resin powder, 2 parts of trans-1, 4-polyisoprene rubber, 2 parts of acrylate rubber, 7 parts of poly (acrylonitrile-butadiene-styrene), 9 parts of dibutyl phthalate, 3 parts of tribasic lead sulfate, 2 parts of calcium stearate, 1 part of nano zinc oxide, 4 parts of nano calcium carbonate, 3 parts of silicon nitride whisker, 2 parts of dicyclopentadiene potassium diformate and 1 part of anti-aging agent.
Preferably, the anti-aging agent is the anti-aging agent 264 and dilauryl thiodipropionate in a mass ratio of 1-3: 1.
Preferably, the anti-aging agent is the anti-aging agent 264 and the dilauryl thiodipropionate in a mass ratio of 2: 1.
The second purpose of the invention is: provides a preparation method of a shape memory material with good memory effect.
In order to achieve the above purpose, the invention provides the following technical scheme:
a preparation method of a shape memory material comprises the following specific steps:
s1: weighing the raw materials in parts by weight;
s2: adding the raw materials into an internal mixer, and mixing in the internal mixer;
s3: and carrying out crushing granulation after banburying, carrying out extrusion molding in a double-screw extruder at the temperature of 150-.
Preferably, in step S2, the blending temperature is 150 ℃ and 160 ℃, and the banburying time is 8-12 min.
Preferably, in step S2, the blending temperature is 155 ℃ and the banburying time is 10 min.
Preferably, in step S3, the curing conditions are as follows: curing at 54-56 deg.C for 1.8-2.2 hr, and then curing at 64-66 deg.C for 1.8-2.2 hr.
Preferably, in step S3, the curing conditions are as follows: curing was carried out for 2h at 55 ℃ and then for 2h at 65 ℃.
The invention has the beneficial effects that:
the material of the invention has good shape memory function by selectively adding trans-1, 4-polyisoprene rubber, acrylate rubber and poly (acrylonitrile-butadiene-styrene), and the memory function of the material is further improved by selecting the second-stage curing temperature and time during preparation; by adding the nano zinc oxide, the nano calcium carbonate, the silicon nitride crystal whisker and the like, the comprehensive performance of the material is improved, and by adding the anti-aging agent, the service life of the material is prolonged.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Example 1
A shape memory material comprises the following raw materials in parts by weight:
88 parts of PVC resin powder, 1 part of trans-1, 4-polyisoprene rubber, 1 part of acrylate rubber, 5 parts of poly (acrylonitrile-butadiene-styrene), 7 parts of dibutyl phthalate, 2 parts of tribasic lead sulfate, 1 part of calcium stearate, 0.5 part of nano zinc oxide, 3 parts of nano calcium carbonate, 2 parts of silicon nitride whisker, 1 part of dicyclopentadiene potassium diformate and 0.5 part of anti-aging agent.
Wherein the anti-aging agent is the anti-aging agent 264 and dilauryl thiodipropionate in a mass ratio of 1: 1.
The preparation method of the shape memory material comprises the following specific steps:
s1: weighing the raw materials in parts by weight;
s2: adding the raw materials into an internal mixer, and mixing in the internal mixer at the mixing temperature of 155 ℃ for 10 min;
s3: banburying, crushing and granulating, extruding and molding in a double-screw extruder at 155 ℃, curing at 54 ℃ for 2.2h, curing at 64 ℃ for 2.2h, and cooling and shaping in water to obtain the finished product.
Example 2
A shape memory material comprises the following raw materials in parts by weight:
100 parts of PVC resin powder, 2 parts of trans-1, 4-polyisoprene rubber, 2 parts of acrylate rubber, 7 parts of poly (acrylonitrile-butadiene-styrene), 9 parts of dibutyl phthalate, 3 parts of tribasic lead sulfate, 2 parts of calcium stearate, 1 part of nano zinc oxide, 4 parts of nano calcium carbonate, 3 parts of silicon nitride whisker, 2 parts of dicyclopentadiene potassium diformate and 1 part of anti-aging agent.
Wherein the anti-aging agent is the anti-aging agent 264 and dilauryl thiodipropionate in a mass ratio of 2: 1.
The preparation method of the shape memory material comprises the following specific steps:
s1: weighing the raw materials in parts by weight;
s2: adding the raw materials into an internal mixer, and mixing in the internal mixer at the mixing temperature of 155 ℃ for 10 min;
s3: banburying, crushing and granulating, extruding and molding in a double-screw extruder at 155 ℃, curing at 55 ℃ for 2h, curing at 65 ℃ for 2h, and cooling and shaping in water to obtain the finished product.
Example 3
A shape memory material comprises the following raw materials in parts by weight:
118 parts of PVC resin powder, 3 parts of trans-1, 4-polyisoprene rubber, 3 parts of acrylate rubber, 8 parts of poly (acrylonitrile-butadiene-styrene), 10 parts of dibutyl phthalate, 5 parts of tribasic lead sulfate, 3 parts of calcium stearate, 1.5 parts of nano zinc oxide, 5 parts of nano calcium carbonate, 4 parts of silicon nitride whisker, 3 parts of dicyclopentadiene potassium diformate and 1.5 parts of anti-aging agent.
Wherein the anti-aging agent is the anti-aging agent 264 and dilauryl thiodipropionate in a mass ratio of 3: 1.
The preparation method of the shape memory material comprises the following specific steps:
s1: weighing the raw materials in parts by weight;
s2: adding the raw materials into an internal mixer, and mixing in the internal mixer at the mixing temperature of 155 ℃ for 10 min;
s3: banburying, crushing and granulating, extruding and molding in a double-screw extruder at 155 ℃, curing at 56 ℃ for 1.8h, curing at 66 ℃ for 1.8h, and cooling and shaping in water to obtain the finished product.
Comparative example 1
A shape memory material comprises the following raw materials in parts by weight:
100 parts of PVC resin powder, 4 parts of trans-1, 4-polyisoprene rubber, 7 parts of poly (acrylonitrile-butadiene-styrene), 9 parts of dibutyl phthalate, 3 parts of tribasic lead sulfate, 2 parts of calcium stearate, 1 part of nano zinc oxide, 4 parts of nano calcium carbonate, 3 parts of silicon nitride whisker, 2 parts of dicyclopentadiene potassium diformate and 1 part of anti-aging agent.
Wherein the anti-aging agent is the anti-aging agent 264 and dilauryl thiodipropionate in a mass ratio of 2: 1.
The shape memory material was prepared as in example 2.
Comparative example 2
A shape memory material comprises the following raw materials in parts by weight:
100 parts of PVC resin powder, 4 parts of acrylate rubber, 7 parts of poly (acrylonitrile-butadiene-styrene), 9 parts of dibutyl phthalate, 3 parts of tribasic lead sulfate, 2 parts of calcium stearate, 1 part of nano zinc oxide, 4 parts of nano calcium carbonate, 3 parts of silicon nitride whisker, 2 parts of dicyclopentadiene potassium diformate and 1 part of anti-aging agent.
Wherein the anti-aging agent is the anti-aging agent 264 and dilauryl thiodipropionate in a mass ratio of 2: 1.
The shape memory material was prepared as in example 2.
Comparative example 3
A shape memory material comprises the following raw materials in parts by weight:
100 parts of PVC resin powder, 2 parts of trans-1, 4-polyisoprene rubber, 2 parts of acrylate rubber, 7 parts of poly (acrylonitrile-butadiene-styrene), 9 parts of dibutyl phthalate, 3 parts of tribasic lead sulfate, 2 parts of calcium stearate, 1 part of nano zinc oxide, 4 parts of nano calcium carbonate, 3 parts of silicon nitride whisker, 2 parts of dicyclopentadiene potassium diformate and 1 part of anti-aging agent.
Wherein the anti-aging agent is the anti-aging agent 264 and dilauryl thiodipropionate in a mass ratio of 2: 1.
The preparation method of the shape memory material comprises the following specific steps:
s1: weighing the raw materials in parts by weight;
s2: adding the raw materials into an internal mixer, and mixing in the internal mixer at the mixing temperature of 155 ℃ for 10 min;
s3: banburying, crushing and granulating, extruding and molding in a double-screw extruder at 155 ℃, solidifying for 4 hours at 65 ℃, and cooling and shaping in water to obtain the finished product.
The pipes obtained in the examples and comparative examples were subjected to bending deformation in a water bath at 75 ℃, then taken out, and after the shape was fixed, the pipes were examined for their recovery deformation at 75 ℃ with the following results:
| item | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Rate of recovery from deformation | 98% | 100% | 99% | 94% | 92% | 95% |
As can be seen from the above table: the trans-1, 4-polyisoprene rubber, the acrylate rubber and the poly (acrylonitrile-butadiene-styrene) in the material have mutual synergistic effect, so that the deformation recovery rate of the material is improved, and the deformation recovery rate of the material can be further improved by selecting the second-stage curing temperature and time.
Claims (9)
1. A shape memory material, characterized by: the feed comprises the following raw materials in parts by weight:
88-118 parts of PVC resin powder, 1-3 parts of trans-1, 4-polyisoprene rubber, 1-3 parts of acrylate rubber, 5-8 parts of poly (acrylonitrile-butadiene-styrene), 7-10 parts of dibutyl phthalate, 2-5 parts of tribasic lead sulfate, 1-3 parts of calcium stearate, 0.5-1.5 parts of nano zinc oxide, 3-5 parts of nano calcium carbonate, 2-4 parts of silicon nitride whisker, 1-3 parts of dicyclopentadiene potassium diformate and 0.5-1.5 parts of anti-aging agent.
2. A shape memory material in accordance with claim 1, wherein: the feed comprises the following raw materials in parts by weight:
100 parts of PVC resin powder, 2 parts of trans-1, 4-polyisoprene rubber, 2 parts of acrylate rubber, 7 parts of poly (acrylonitrile-butadiene-styrene), 9 parts of dibutyl phthalate, 3 parts of tribasic lead sulfate, 2 parts of calcium stearate, 1 part of nano zinc oxide, 4 parts of nano calcium carbonate, 3 parts of silicon nitride whisker, 2 parts of dicyclopentadiene potassium diformate and 1 part of anti-aging agent.
3. A shape memory material in accordance with claim 1, wherein:
the anti-aging agent is composed of an anti-aging agent 264 and dilauryl thiodipropionate in a mass ratio of 1-3: 1.
4. A shape memory material in accordance with claim 3, wherein:
the anti-aging agent is composed of an anti-aging agent 264 and dilauryl thiodipropionate in a mass ratio of 2: 1.
5. A method of preparing a shape memory material according to any one of claims 1 to 4, wherein: the method comprises the following specific steps:
s1: weighing the raw materials in parts by weight;
s2: adding the raw materials into an internal mixer, and mixing in the internal mixer;
s3: and carrying out crushing granulation after banburying, carrying out extrusion molding in a double-screw extruder at the temperature of 150-.
6. The method for preparing a shape memory material according to claim 5, wherein: in step S2, the blending temperature is 150 ℃ and 160 ℃, and the banburying time is 8-12 min.
7. The method for preparing a shape memory material according to claim 5, wherein: in step S2, the blending temperature is 155 ℃, and the banburying time is 10 min.
8. The method for preparing a shape memory material according to claim 5, wherein: in step S3, the curing conditions are as follows: curing at 54-56 deg.C for 1.8-2.2 hr, and then curing at 64-66 deg.C for 1.8-2.2 hr.
9. The method for preparing a shape memory material according to claim 5, wherein: in step S3, the curing conditions are as follows: curing was carried out for 2h at 55 ℃ and then for 2h at 65 ℃.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010458793.7A CN111534025A (en) | 2020-05-27 | 2020-05-27 | Shape memory material and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010458793.7A CN111534025A (en) | 2020-05-27 | 2020-05-27 | Shape memory material and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0665460A (en) * | 1992-08-21 | 1994-03-08 | Tosoh Corp | Shape memory resin material |
| CN104004304A (en) * | 2014-06-23 | 2014-08-27 | 北京化工大学 | PVC material with shape memory function |
| CN107987416A (en) * | 2017-11-28 | 2018-05-04 | 永高股份有限公司 | A kind of composite material of shape memory for the quick pipe-repairing of no-dig technique |
| CN110982191A (en) * | 2019-12-05 | 2020-04-10 | 浙江工业大学之江学院 | Shape memory material and preparation method thereof |
-
2020
- 2020-05-27 CN CN202010458793.7A patent/CN111534025A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0665460A (en) * | 1992-08-21 | 1994-03-08 | Tosoh Corp | Shape memory resin material |
| CN104004304A (en) * | 2014-06-23 | 2014-08-27 | 北京化工大学 | PVC material with shape memory function |
| CN107987416A (en) * | 2017-11-28 | 2018-05-04 | 永高股份有限公司 | A kind of composite material of shape memory for the quick pipe-repairing of no-dig technique |
| CN110982191A (en) * | 2019-12-05 | 2020-04-10 | 浙江工业大学之江学院 | Shape memory material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 何领好，王明花主编: "《功能高分子材料》", 31 August 2016, 武汉：华中科技大学出版社 * |
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Application publication date: 20200814 |