CN112250860A - Method for modifying MC nylon engineering plastic by organic silicon - Google Patents
Method for modifying MC nylon engineering plastic by organic silicon Download PDFInfo
- Publication number
- CN112250860A CN112250860A CN202010980211.1A CN202010980211A CN112250860A CN 112250860 A CN112250860 A CN 112250860A CN 202010980211 A CN202010980211 A CN 202010980211A CN 112250860 A CN112250860 A CN 112250860A
- Authority
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- China
- Prior art keywords
- nylon
- vinyl
- organic silicon
- terminated
- caprolactam
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 239000004677 Nylon Substances 0.000 title claims abstract description 64
- 229920001778 nylon Polymers 0.000 title claims abstract description 64
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 35
- 239000010703 silicon Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 23
- 229920006351 engineering plastic Polymers 0.000 title claims abstract description 17
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims abstract description 38
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- -1 polysiloxane Polymers 0.000 claims abstract description 18
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 12
- 238000010539 anionic addition polymerization reaction Methods 0.000 claims abstract description 10
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 8
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims abstract description 5
- 239000000178 monomer Substances 0.000 claims abstract description 4
- 150000003951 lactams Chemical class 0.000 claims abstract description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 11
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 11
- 230000005251 gamma ray Effects 0.000 claims description 10
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011347 resin Substances 0.000 abstract description 5
- 229920005989 resin Polymers 0.000 abstract description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract description 5
- 229920002554 vinyl polymer Polymers 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 229920002292 Nylon 6 Polymers 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000004870 electrical engineering Methods 0.000 description 1
- 229920006258 high performance thermoplastic Polymers 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
- C08G77/455—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences containing polyamide, polyesteramide or polyimide sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2270/00—Compositions for creating interpenetrating networks
Abstract
The invention discloses a method for preparing organic silicon modified MC nylon engineering plastic, which comprises the following steps: s1, introducing vinyl-terminated organosilicon into caprolactam anion polymerization: at the temperature of 130 ℃ and 140 ℃, after lactam monomers are activated and dehydrated in vacuum, the mass ratio of caprolactam to vinyl-terminated organosilicon is 100: and (3) adding the vinyl-terminated organic silicon into a reactor according to the proportion of 10-30, uniformly dispersing the vinyl-terminated organic silicon, and finishing the polymerization reaction of MC nylon according to a caprolactam anionic polymerization process. The invention adopts vinyl-terminated siloxane resin to disperse in caprolactam anion polymerization process, introduces vinyl-terminated siloxane into MC nylon, and then initiates vinyl end radical polymerization through secondary irradiation to form an interpenetrating network structure of polysiloxane and MC nylon to prepare the organic silicon modified MC nylon.
Description
Technical Field
The invention relates to the technical field of engineering plastic modification, in particular to a method for modifying MC nylon engineering plastic by organic silicon.
Background
MC nylon 6 is a thermoplastic polymer obtained by polymerizing caprolactam monomers by adopting an anionic polymerization mechanism, and because of the polarity of a characteristic functional group amide structure in a molecular chain structure, the intermolecular force is large, so that the crystallinity of the MC nylon 6 is high. Therefore, the MC nylon 6 has high rigidity, high mechanical strength and good wear resistance. The high-performance thermoplastic elastomer is widely applied to the fields of mechanical manufacture, electrical engineering and the like as an important engineering plastic. However, MC nylon 6 has the problem of easy water absorption to cause water plasticization deformation of MC nylon products, and MC nylon needs to be subjected to hydrophobic modification to reduce the water absorption and improve the stability of the service performance in a damp and hot environment; the organic silicon resin has excellent hydrophobicity and is widely applied to the fields of chemical industry, water proofing, sealing and the like.
The invention provides a method for modifying MC nylon engineering plastic by using hydrophobic organic silicon resin, which solves the problem that MC nylon 6 is easy to absorb water to cause water plasticization deformation of an MC nylon product.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a method for modifying MC nylon engineering plastics by organic silicon, which has the advantage of reducing the water absorption of MC nylon products and solves the problem of water plasticization deformation of the MC nylon products caused by the easy water absorption of MC nylon 6.
(II) technical scheme
1. In order to achieve the purpose, the invention provides the following technical scheme: a method for preparing organic silicon modified MC nylon engineering plastic comprises the following steps:
s1, introducing vinyl-terminated organosilicon into caprolactam anion polymerization: at the temperature of 130 ℃ and 140 ℃, after lactam monomers are activated and dehydrated in vacuum, the mass ratio of caprolactam to vinyl-terminated organosilicon is 100: adding vinyl-terminated organic silicon into a reactor according to the proportion of 10-30, uniformly dispersing the vinyl-terminated organic silicon, and finishing MC nylon polymerization according to a caprolactam anionic polymerization process;
and S2, carrying out secondary gamma ray irradiation on MC nylon containing vinyl-terminated organic silicon to initiate free radical polymerization to form an interpenetrating network structure of polysiloxane and MC nylon, and preparing the organic silicon modified MC nylon.
Preferably, the vinyl-terminated silicone is vinyl-terminated polydimethylsiloxane and vinyl-terminated polymethylvinylsiloxane.
Preferably, the gamma ray irradiation dose is 20-50 kGy.
(III) advantageous effects
Compared with the prior art, the invention provides a method for modifying MC nylon engineering plastics by organic silicon, which has the following beneficial effects:
the invention discloses a method for modifying MC nylon engineering plastic by organic silicon, which comprises the steps of dispersing vinyl-terminated siloxane resin into caprolactam anion polymerization, introducing the vinyl-terminated siloxane into MC nylon, initiating vinyl-terminated radical polymerization by secondary irradiation to form an interpenetrating network structure of polysiloxane and MC nylon, preparing the organic silicon modified MC nylon, improving the water absorption of the MC nylon by utilizing the hydrophobicity of the organic silicon, reducing the plasticizing effect of water on the MC nylon, and improving the stability of the service performance of the MC nylon in a humid and hot environment.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples.
Example 1:
the invention provides a method for modifying MC nylon engineering plastic by organic silicon, which comprises the following steps:
s1, weighing 100g of caprolactam monomer, adding the caprolactam monomer into a reactor, heating, melting, activating and vacuum dehydrating at the temperature of 130-140 ℃, synchronously adding 20 g of vinyl polydimethylsiloxane with an anionic initiator toluene diisocyanate, and rapidly centrifuging, dispersing and heating to perform caprolactam polymerization reaction to obtain an organosilicon/MC nylon preform;
s2, the preparation of the modified MC nylon with the interpenetrating network structure of the polyorganosiloxane and the MC nylon is realized by a secondary polymerization method: and (3) at room temperature, carrying out gamma ray irradiation on the organic silicon/MC nylon prefabricated product to complete second polymerization, and carrying out free radical polymerization on the vinyl-terminated polydimethylsiloxane pre-embedded in the MC nylon to obtain the modified MC nylon with the interpenetrating network structure of the polyvinyl-terminated polydimethylsiloxane and the MC nylon.
Specifically, the irradiation dose of the gamma ray is 20-50 kGy.
Example 2:
the invention provides a method for modifying MC nylon engineering plastic by organic silicon, which comprises the following steps:
s1, weighing 100g of caprolactam monomer, adding the caprolactam monomer into a reactor, heating, melting, activating and vacuum dehydrating at the temperature of 130-140 ℃, synchronously adding 10 g of vinyl polydimethylsiloxane with an anionic initiator toluene diisocyanate, and rapidly centrifuging, dispersing and heating to perform caprolactam polymerization reaction to obtain an organosilicon/MC nylon preform;
s2, the preparation of the modified MC nylon with the interpenetrating network structure of the polyorganosiloxane and the MC nylon is realized by a secondary polymerization method: and (3) at room temperature, carrying out gamma ray irradiation on the organic silicon/MC nylon prefabricated product to complete second polymerization, and carrying out free radical polymerization on the vinyl-terminated polydimethylsiloxane pre-embedded in the MC nylon to obtain the modified MC nylon with the interpenetrating network structure of the polyvinyl-terminated polydimethylsiloxane and the MC nylon.
Specifically, the irradiation dose of the gamma ray is 20-50 kGy.
Example 3:
the invention provides a method for modifying MC nylon engineering plastic by organic silicon, which comprises the following steps:
s1, weighing 100g of caprolactam monomer, adding the caprolactam monomer into a reactor, heating, melting, activating and vacuum dehydrating at the temperature of 130-140 ℃, synchronously adding 30 g of vinyl polydimethylsiloxane with an anionic initiator toluene diisocyanate, and rapidly centrifuging, dispersing and heating to perform caprolactam polymerization reaction to obtain an organosilicon/MC nylon preform;
s2, the preparation of the modified MC nylon with the interpenetrating network structure of the polyorganosiloxane and the MC nylon is realized by a secondary polymerization method: and (3) at room temperature, carrying out gamma ray irradiation on the organic silicon/MC nylon prefabricated product to complete second polymerization, and carrying out free radical polymerization on the vinyl-terminated polydimethylsiloxane pre-embedded in the MC nylon to obtain the modified MC nylon with the interpenetrating network structure of the polyvinyl-terminated polydimethylsiloxane and the MC nylon.
Specifically, the irradiation dose of the gamma ray is 20-50 kGy.
In conclusion, the invention adopts the vinyl-terminated siloxane resin to disperse in the caprolactam anion polymerization process, introduces the vinyl-terminated siloxane into the MC nylon, and then initiates vinyl end group free radical polymerization through secondary irradiation to form an interpenetrating network structure of polysiloxane and the MC nylon to prepare the organic silicon modified MC nylon, and utilizes the hydrophobicity of the organic silicon to improve the water absorption of the MC nylon and reduce the plasticizing effect of water on the MC nylon.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, but any modifications or equivalent variations made according to the technical spirit of the present invention are within the scope of the present invention as claimed.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (3)
1. The method for preparing the organic silicon modified MC nylon engineering plastic is characterized by comprising the following steps of:
s1, introducing vinyl-terminated organosilicon into caprolactam anion polymerization: at the temperature of 130 ℃ and 140 ℃, after lactam monomers are activated and dehydrated in vacuum, the mass ratio of caprolactam to vinyl-terminated organosilicon is 100: adding vinyl-terminated organic silicon into a reactor according to the proportion of 10-30, uniformly dispersing the vinyl-terminated organic silicon, and finishing MC nylon polymerization according to a caprolactam anionic polymerization process;
and S2, carrying out secondary gamma ray irradiation on MC nylon containing vinyl-terminated organic silicon to initiate free radical polymerization to form an interpenetrating network structure of polysiloxane and MC nylon, and preparing the organic silicon modified MC nylon.
2. The method for modifying MC nylon engineering plastic by organic silicon according to claim 1, wherein the vinyl-terminated organic silicon is vinyl-terminated polydimethylsiloxane and vinyl-terminated polymethylvinylsiloxane.
3. The method for modifying MC nylon engineering plastic by organic silicon according to claim 1, wherein the gamma ray irradiation dose is 20-50 kGy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010980211.1A CN112250860A (en) | 2020-09-17 | 2020-09-17 | Method for modifying MC nylon engineering plastic by organic silicon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010980211.1A CN112250860A (en) | 2020-09-17 | 2020-09-17 | Method for modifying MC nylon engineering plastic by organic silicon |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112250860A true CN112250860A (en) | 2021-01-22 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010980211.1A Pending CN112250860A (en) | 2020-09-17 | 2020-09-17 | Method for modifying MC nylon engineering plastic by organic silicon |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112250860A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6329462B1 (en) * | 1999-06-18 | 2001-12-11 | Eastman Chemical Company | Nylon 6/silicone blends |
| CN103276584A (en) * | 2013-05-27 | 2013-09-04 | 江苏纺科新复合材料有限公司 | Method for to preparing polyolefin elastic fiber by adopting irradiation technology |
| CN104829832A (en) * | 2015-02-11 | 2015-08-12 | 杭州师范大学 | Preparation method of organic-silicone-modified flame-retarding nylon-6 |
| CN107011651A (en) * | 2017-04-28 | 2017-08-04 | 湖南工业大学 | A kind of nano composite material of POSS/ nylon monomer-cast nylons 6 and its preparation method and application |
| CN109438820A (en) * | 2018-09-27 | 2019-03-08 | 中广核高新核材科技（苏州）有限公司 | Long-life irradiation cross-linking low smoke halogen-free fire retardant polyolefin cable material and preparation method thereof |
| CN109651693A (en) * | 2018-12-26 | 2019-04-19 | 无锡杰科塑业有限公司 | Micro- interpenetrating networks crosslinking type low-smoke halogen-free flame-retardant CABLE MATERIALS and preparation method thereof |
-
2020
- 2020-09-17 CN CN202010980211.1A patent/CN112250860A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6329462B1 (en) * | 1999-06-18 | 2001-12-11 | Eastman Chemical Company | Nylon 6/silicone blends |
| CN103276584A (en) * | 2013-05-27 | 2013-09-04 | 江苏纺科新复合材料有限公司 | Method for to preparing polyolefin elastic fiber by adopting irradiation technology |
| CN104829832A (en) * | 2015-02-11 | 2015-08-12 | 杭州师范大学 | Preparation method of organic-silicone-modified flame-retarding nylon-6 |
| CN107011651A (en) * | 2017-04-28 | 2017-08-04 | 湖南工业大学 | A kind of nano composite material of POSS/ nylon monomer-cast nylons 6 and its preparation method and application |
| CN109438820A (en) * | 2018-09-27 | 2019-03-08 | 中广核高新核材科技（苏州）有限公司 | Long-life irradiation cross-linking low smoke halogen-free fire retardant polyolefin cable material and preparation method thereof |
| CN109651693A (en) * | 2018-12-26 | 2019-04-19 | 无锡杰科塑业有限公司 | Micro- interpenetrating networks crosslinking type low-smoke halogen-free flame-retardant CABLE MATERIALS and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| NILAY KANTI PRAMANIK ET AL: "Radiation processing of nylon 6 by gamma rays and improvement of its physico-mechanical properties" * |
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| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210122 |
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| RJ01 | Rejection of invention patent application after publication |