CN112852179A - High-strength polyethylene modified resin adhesive and preparation method thereof - Google Patents
High-strength polyethylene modified resin adhesive and preparation method thereof Download PDFInfo
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- CN112852179A CN112852179A CN202011606820.7A CN202011606820A CN112852179A CN 112852179 A CN112852179 A CN 112852179A CN 202011606820 A CN202011606820 A CN 202011606820A CN 112852179 A CN112852179 A CN 112852179A
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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
- C08L101/00—Compositions of unspecified macromolecular compounds
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/02—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements ultrasonic or sonic; Corona discharge
- D06M10/025—Corona discharge or low temperature plasma
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/20—Polyalkenes, polymers or copolymers of compounds with alkenyl groups bonded to aromatic groups
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention discloses a preparation method of a high-strength polyethylene modified resin adhesive, which comprises the following steps: s1, carrying out surface treatment on the ultrahigh molecular weight polyethylene fiber; s2, preparing ultra-high molecular weight polyethylene chopped fibers; and S3, mixing the ultra-high molecular weight polyethylene chopped fibers with the basic resin glue solution. The preparation method of the high-strength polyethylene modified resin adhesive is completed on the premise of not changing the basic structure of the resin adhesive, namely on the premise of not increasing the subsequent processing difficulty. The high-strength polyethylene modified resin adhesive prepared by the method has good breaking strength, tensile modulus and elongation at break, so that the high-strength polyethylene modified resin adhesive has better energy absorption performance.
Description
Technical Field
The invention relates to the technical field of resin adhesives, in particular to a high-strength polyethylene modified resin adhesive and a preparation method thereof.
Background
The high-strength polyethylene non-woven cloth is the main raw material of the prior light bulletproof product such as body armor, bulletproof helmet and bulletproof plate, and the performance of the high-strength polyethylene non-woven cloth directly influences the bulletproof performance of the final bulletproof product. The high-strength polyethylene non-woven fabric is an organic composite material formed by ultra-high molecular weight polyethylene fibers, resin glue and auxiliary materials, wherein the properties (such as breaking strength, tensile modulus and the like) of the ultra-high molecular weight polyethylene fibers and the properties (such as breaking strength, tensile modulus, breaking elongation, tear resistance and the like) of the resin glue have important influence on the properties of the high-strength polyethylene non-woven fabric.
At present, the properties of the adhesive film, such as breaking strength, tensile modulus and the like, can be adjusted by changing the molecular structure of the resin adhesive matrix, but if the strength or modulus is improved due to the change of the molecular structure, the melting and vulcanizing temperature of the resin is correspondingly improved, which brings difficulty to the subsequent processing of the high-strength polyethylene non-woven fabric. Mainly because the subsequent processing process of the high-strength polyethylene non-woven cloth usually needs the melting of resin glue and the physical crosslinking, thereby improving the performance of the glue film.
Therefore, a preparation method capable of improving the mechanical properties of the resin adhesive film without changing the basic structure of the resin adhesive is needed.
Disclosure of Invention
The present invention is directed to a high-strength polyethylene modified resin adhesive and a method for preparing the same, which solves one or more of the above-mentioned problems of the prior art.
On one hand, the preparation method of the high-strength polyethylene modified resin adhesive provided by the invention comprises the following steps:
s1, carrying out surface treatment on the ultrahigh molecular weight polyethylene fiber;
s2, preparing ultra-high molecular weight polyethylene chopped fibers;
and S3, mixing the ultra-high molecular weight polyethylene chopped fibers with the basic resin glue solution.
In certain embodiments, the ultra-high molecular weight polyethylene fibers have a tenacity of greater than or equal to 10cN/dtex, a modulus of greater than or equal to 300cN/dtex, an elongation at break of greater than or equal to 2.5%, a length of less than or equal to 25mm, and a filament diameter of less than or equal to 15 μm.
In some embodiments, the ultra high molecular weight polyethylene fibers have a tenacity of greater than or equal to 15cN/dtex, a modulus of greater than or equal to 500cN/dtex, an elongation at break of greater than or equal to 2.8%, a length of greater than or equal to 1mm, and a filament diameter of less than or equal to 10 μm.
In some embodiments, the ultra high molecular weight polyethylene fibers have a breaking strength of greater than or equal to 20cN/dtex, a modulus of greater than or equal to 800cN/dtex, an elongation at break of greater than or equal to 3.2%, a length of greater than or equal to 5mm, and a filament diameter of less than or equal to 5 μm.
In certain embodiments, the surface treatment in step S1 includes chemical grafting modification, surface chemical etching, or surface low temperature plasma treatment.
Wherein: the interface bonding force of the fiber and the resin adhesive can be improved through surface treatment.
In some embodiments, the surface treatment in step S1 includes a low-temperature plasma treatment of the surface, specifically: and (3) carrying out plasma irradiation treatment on the surface of the ultra-high molecular weight polyethylene fiber by using a low-temperature plasma treatment machine, wherein the treatment time is less than or equal to 5 min.
In certain embodiments, step S2 is specifically:
the ultra-high molecular weight polyethylene fiber subjected to the surface treatment in the step S1 is made into chopped ultra-high molecular weight polyethylene fiber with the length of 0.1-25mm by using a grinding and crushing or cutting method.
In certain embodiments, the chopped ultrahigh molecular weight polyethylene fibers have a length of from 1 to 10 mm.
In certain embodiments, step S3 is specifically:
dispersing the chopped ultrahigh molecular weight polyethylene fibers prepared in the step S2 in deionized water, adding a surfactant, and fully and uniformly mixing the fibers by using a grinding mill to prepare fiber slurry;
and adding the fiber slurry into the matrix resin glue solution to prepare the modified resin glue.
Wherein: taking a proper amount of matrix resin glue solution, and gradually adding the fiber pulp while stirring. And after the short fibers are completely added, continuously stirring until the short fibers are uniformly dispersed in the whole glue solution system to prepare the high-strength polyethylene modified resin glue.
In certain embodiments, the matrix resin cement is an oily system or an aqueous system.
In certain embodiments, the surfactant added in step S3 is 1-3% by weight of the deionized water and the chopped ultrahigh molecular weight polyethylene fibers are less than or equal to 10% by weight of the deionized water.
On the other hand, the high-strength polyethylene modified resin adhesive provided by the invention is prepared by the preparation method, and the preparation method comprises the following steps:
s1, carrying out surface treatment on the ultrahigh molecular weight polyethylene fiber;
s2, preparing ultra-high molecular weight polyethylene chopped fibers;
and S3, mixing the ultra-high molecular weight polyethylene chopped fibers with the basic resin glue solution.
In some embodiments, the high-strength polyethylene modified resin glue consists of a base resin glue solution and high-strength polyethylene fibers, wherein the solid content of the base resin glue solution is 10-80% and the content of the ultrahigh-molecular-weight polyethylene fibers is 0.1-5% in percentage by weight.
In some embodiments, the high-strength polyethylene modified resin adhesive consists of a matrix resin adhesive solution and high-strength polyethylene fibers, and the solid content of the matrix resin adhesive solution is 30-5% by weight percent; the content of the ultra-high molecular weight polyethylene fiber is 0.1-5%.
Has the advantages that: the preparation method of the high-strength polyethylene modified resin adhesive is completed on the premise of not changing the basic structure of the resin adhesive, namely on the premise of not increasing the subsequent processing difficulty. The high-strength polyethylene modified resin adhesive prepared by the method has good breaking strength, tensile modulus and elongation at break, so that the high-strength polyethylene modified resin adhesive has better energy absorption performance.
Detailed Description
The present invention will be described in further detail below with reference to embodiments.
Example 1
A preparation method of high-strength polyethylene modified resin adhesive comprises the following steps:
s1, carrying out surface treatment on the ultrahigh molecular weight polyethylene fiber:
carrying out plasma irradiation treatment on the surface of the ultra-high molecular weight polyethylene fiber by using a low-temperature plasma treatment machine for 5 min;
s2, preparing ultra-high molecular weight polyethylene chopped fibers:
preparing the treated ultrahigh molecular weight polyethylene fiber filaments into chopped ultrahigh molecular weight polyethylene fibers with the length of 25mm by using a grinding and crushing or cutting method;
s3, mixing the ultra-high molecular weight polyethylene chopped fibers with the basic resin glue solution:
adding the ultra-high molecular weight polyethylene chopped fibers into deionized water according to a certain concentration, adding 1% of surfactant, and fully and uniformly mixing by means of a grinding mill and the like to prepare uniform slurry. The chopped fibers account for 10 percent of the weight of the deionized water, and the surfactant accounts for 1 percent of the weight of the deionized water;
taking a proper amount of matrix resin glue solution, and gradually adding the fiber pulp while stirring. And after the short fibers are completely added, continuously stirring until the short fibers are uniformly dispersed in the whole glue solution system to prepare the high-strength polyethylene modified resin glue.
Wherein: the breaking strength of the ultra-high molecular weight polyethylene fiber is 20cN/dtex, the modulus is 800cN/dtex, the elongation at break is 3.2%, the length is 5mm, and the monofilament diameter is 5 um.
The high-strength polyethylene modified resin adhesive consists of a matrix resin adhesive solution and high-strength polyethylene fibers, wherein the solid content of the matrix resin adhesive solution is 30 percent in percentage by weight; the content of the ultra-high molecular weight polyethylene fiber is 0.1%.
Example 2
A preparation method of high-strength polyethylene modified resin adhesive comprises the following steps:
s1, carrying out surface treatment on the ultrahigh molecular weight polyethylene fiber:
carrying out plasma irradiation treatment on the surface of the ultra-high molecular weight polyethylene fiber by using a low-temperature plasma treatment machine for 3 min;
s2, preparing ultra-high molecular weight polyethylene chopped fibers:
grinding or cutting the treated ultra-high molecular weight polyethylene fiber filaments into chopped ultra-high molecular weight polyethylene fibers with the length of 10 mm;
s3, mixing the ultra-high molecular weight polyethylene chopped fibers with the basic resin glue solution:
adding the ultra-high molecular weight polyethylene chopped fibers into deionized water according to a certain concentration, adding 2% of surfactant, and fully and uniformly mixing by means of a grinding mill and the like to prepare uniform slurry. The chopped fibers account for 5% of the deionized water by weight, and the surfactant accounts for 2% of the deionized water by weight;
taking a proper amount of matrix resin glue solution, and gradually adding the fiber pulp while stirring. And after the short fibers are completely added, continuously stirring until the short fibers are uniformly dispersed in the whole glue solution system to prepare the high-strength polyethylene modified resin glue.
Wherein: the breaking strength of the ultra-high molecular weight polyethylene fiber is 30cN/dtex, the modulus is 900cN/dtex, the elongation at break is 4.2%, the length is 6mm, and the monofilament diameter is 3 um.
The high-strength polyethylene modified resin adhesive consists of a matrix resin adhesive solution and high-strength polyethylene fibers, wherein the solid content of the matrix resin adhesive solution is 15 percent in percentage by weight; the content of the ultra-high molecular weight polyethylene fiber is 2%.
Example 3
A preparation method of high-strength polyethylene modified resin adhesive comprises the following steps:
s1, carrying out surface treatment on the ultrahigh molecular weight polyethylene fiber:
carrying out plasma irradiation treatment on the surface of the ultra-high molecular weight polyethylene fiber by using a low-temperature plasma treatment machine for 2 min;
s2, preparing ultra-high molecular weight polyethylene chopped fibers:
grinding or cutting the treated ultra-high molecular weight polyethylene fiber filaments into chopped ultra-high molecular weight polyethylene fibers with the length of 1 mm;
s3, mixing the ultra-high molecular weight polyethylene chopped fibers with the basic resin glue solution:
adding the ultra-high molecular weight polyethylene chopped fibers into deionized water according to a certain concentration, adding 3% of surfactant, and fully and uniformly mixing by means of a grinding mill and the like to prepare uniform slurry. The chopped fibers account for 1% of the weight of the deionized water, and the surfactant accounts for 3% of the weight of the deionized water;
taking a proper amount of matrix resin glue solution, and gradually adding the fiber pulp while stirring. And after the short fibers are completely added, continuously stirring until the short fibers are uniformly dispersed in the whole glue solution system to prepare the high-strength polyethylene modified resin glue.
Wherein: the breaking strength of the ultra-high molecular weight polyethylene fiber is 40cN/dtex, the modulus is 1000cN/dtex, the elongation at break is 5%, the length is 7mm, and the monofilament diameter is 2 um.
The high-strength polyethylene modified resin adhesive consists of a matrix resin adhesive solution and high-strength polyethylene fibers, wherein the solid content of the matrix resin adhesive solution is 5 percent in percentage by weight; the content of the ultra-high molecular weight polyethylene fiber is 5%.
Comparative example 1
The unmodified ultra-high molecular weight polyethylene fiber and the basic resin with the same specification in the example 1 are mixed, and the concrete steps are as follows:
adding unmodified ultra-high molecular weight polyethylene fibers into deionized water according to a certain concentration, adding 1% of surfactant, and fully and uniformly mixing by means of a grinding mill and the like to prepare uniform slurry. The weight ratio of unmodified ultra-high molecular weight polyethylene fiber to deionized water is 10%, and the weight ratio of surfactant to deionized water is 1%;
taking a proper amount of matrix resin glue solution, and gradually adding the fiber pulp while stirring. And after the short fibers are completely added, continuously stirring until the short fibers are uniformly dispersed in the whole glue solution system to prepare the high-strength polyethylene modified resin glue.
Performance testing
The high-strength polyethylene modified resin adhesives prepared in the above examples 1 to 3 and comparative example 1 were made into adhesive films with thickness of 0.5mm and width of 4mm, and the breaking strength, tensile modulus (100% constant elongation) and elongation at break were measured according to the GB/T528 standard, and the specific test results are shown in Table 1:
TABLE 1
| Numbering | Breaking Strength (MPa) | Tensile modulus (MPa) | Elongation at Break (%) |
| Example 1 | 24.5 | 5.8 | 340 |
| Example 2 | 29.2 | 6.5 | 356 |
| Example 3 | 33.8 | 7.6 | 370 |
| Comparative example 1 | 23.6 | 5.6 | 332 |
As can be seen from table 1, the high-strength polyethylene modified resin adhesives prepared in examples 1 to 3 of the present invention have higher breaking strength, tensile modulus and elongation at break than those of comparative example 1.
In summary, the following steps: the preparation method of the high-strength polyethylene modified resin adhesive is completed on the premise of not changing the basic structure of the resin adhesive, namely on the premise of not increasing the subsequent processing difficulty. The high-strength polyethylene modified resin adhesive prepared by the method has good breaking strength, tensile modulus and elongation at break, so that the high-strength polyethylene modified resin adhesive has better energy absorption performance.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various changes and modifications can be made without departing from the inventive concept of the present invention, and these should be considered as within the scope of the present invention.
Claims (10)
1. The preparation method of the high-strength polyethylene modified resin adhesive is characterized by comprising the following steps:
s1, carrying out surface treatment on the ultrahigh molecular weight polyethylene fiber;
s2, preparing ultra-high molecular weight polyethylene chopped fibers;
and S3, mixing the ultra-high molecular weight polyethylene chopped fibers with the basic resin glue solution.
2. The preparation method of claim 1, wherein the ultra-high molecular weight polyethylene fiber has a breaking strength of 10cN/dtex or more, a modulus of 300cN/dtex or more, an elongation at break of 2.5% or more, a length of 25mm or less, and a monofilament diameter of 15um or less; preferably, the breaking strength is more than or equal to 15cN/dtex, the modulus is more than or equal to 500cN/dtex, the elongation at break is more than or equal to 2.8 percent, the length is more than or equal to 1mm, and the diameter of the monofilament is less than or equal to 10 um; more preferably, the breaking strength is more than or equal to 20cN/dtex, the modulus is more than or equal to 800cN/dtex, the elongation at break is more than or equal to 3.2 percent, the length is more than or equal to 5mm, and the diameter of the monofilament is less than or equal to 5 um.
3. The method according to claim 1, wherein the surface treatment in step S1 includes chemical grafting modification, surface chemical etching, or surface low-temperature plasma treatment.
4. The production method according to claim 1, wherein the surface treatment in step S1 includes surface low-temperature plasma treatment, specifically: and (3) carrying out plasma irradiation treatment on the surface of the ultra-high molecular weight polyethylene fiber by using a low-temperature plasma treatment machine, wherein the treatment time is less than or equal to 5 min.
5. The method according to claim 1, wherein step S2 specifically comprises:
the ultra-high molecular weight polyethylene fibers subjected to the surface treatment in the step S1 are made into chopped ultra-high molecular weight polyethylene fibers having a length of 0.1 to 25mm by a grinding, pulverizing or cutting method, preferably, the chopped ultra-high molecular weight polyethylene fibers have a length of 1 to 10 mm.
6. The method according to claim 1, wherein step S3 specifically comprises:
dispersing the chopped ultrahigh molecular weight polyethylene fibers prepared in the step S2 in deionized water, adding a surfactant, and fully and uniformly mixing the fibers by using a grinding mill to prepare fiber slurry;
and adding the fiber slurry into the matrix resin glue solution to prepare the modified resin glue.
7. The method according to claim 6, wherein the base resin dope is an oily system or an aqueous system.
8. The method of claim 6, wherein the surfactant added in step S3 is 1-3% by weight of the deionized water, and the chopped ultra-high molecular weight polyethylene fibers are less than or equal to 10% by weight of the deionized water.
9. The high-strength polyethylene modified resin adhesive is characterized by being prepared by the preparation method of any one of claims 1 to 8.
10. The high-strength polyethylene modified resin adhesive according to claim 9, which is composed of a matrix resin adhesive solution and high-strength polyethylene fibers, wherein the solid content of the matrix resin adhesive solution is 10-80% by weight, preferably 30-5% by weight; the content of the ultra-high molecular weight polyethylene fiber is 0.1-5%.
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| CN202011606820.7A CN112852179A (en) | 2020-12-28 | 2020-12-28 | High-strength polyethylene modified resin adhesive and preparation method thereof |
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| US20160136926A1 (en) * | 2013-06-20 | 2016-05-19 | Zhengzhou Zhongyuan Defense Material Co., Ltd | Non-Weft Cloth, Manufacturing Method Therefor, And Non-Weft Cloth Product |
| CN107245197A (en) * | 2017-06-23 | 2017-10-13 | 安徽长青藤新材料有限公司 | Fiber reinforcement polystyrene foam plate |
| CN108395675A (en) * | 2018-03-09 | 2018-08-14 | 天津工业大学 | A kind of tannic acid modified superhigh molecular weight polyethylene fibers and its composite material and preparation method thereof |
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2020
- 2020-12-28 CN CN202011606820.7A patent/CN112852179A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160136926A1 (en) * | 2013-06-20 | 2016-05-19 | Zhengzhou Zhongyuan Defense Material Co., Ltd | Non-Weft Cloth, Manufacturing Method Therefor, And Non-Weft Cloth Product |
| CN107245197A (en) * | 2017-06-23 | 2017-10-13 | 安徽长青藤新材料有限公司 | Fiber reinforcement polystyrene foam plate |
| CN108395675A (en) * | 2018-03-09 | 2018-08-14 | 天津工业大学 | A kind of tannic acid modified superhigh molecular weight polyethylene fibers and its composite material and preparation method thereof |
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| 于占江等主编: "《国家示范性专业重点规划教材 摩擦材料生产工艺》", 31 January 2018, 天津大学出版社 * |
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| 张兴鲁等: "超高分子量聚乙烯纤维增强复合材料研究进展", 《玻璃钢/复合材料增刊（第十七届玻璃钢/复合材料学术年会论文集）》 * |
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Application publication date: 20210528 |