CN102964822A - Silicon rubber toughened and modified nylon resin and preparation method thereof - Google Patents
Silicon rubber toughened and modified nylon resin and preparation method thereof Download PDFInfo
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- CN102964822A CN102964822A CN2012105339272A CN201210533927A CN102964822A CN 102964822 A CN102964822 A CN 102964822A CN 2012105339272 A CN2012105339272 A CN 2012105339272A CN 201210533927 A CN201210533927 A CN 201210533927A CN 102964822 A CN102964822 A CN 102964822A
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Abstract
The invention discloses a silicon rubber toughened and modified nylon resin and a preparation method thereof. According to the preparation method of the silicon rubber toughened and modified nylon resin, compatibilization and toughening are synchronously performed, silicon rubber can be evenly dispersed in nylon through one-step processing, and the silicon rubber of a disperse phase can be dynamically vulcanized, thereby realizing the toughening of the nylon. The processing technique disclosed by the invention is simple; and compared with the method for toughening nylon by using other types of rubber or elastomer, the nylon prepared by the method disclosed by the invention has excellent properties such as favorable heat resistance, oil resistance, shock resistance and the like, and can be used in the fields of automobiles, buildings, electronics and electrical and the like.
Description
Technical field
The present invention relates to a kind of nylon resin and preparation method thereof, particularly nylon resin of a kind of toughened with silicon rubber modification and preparation method thereof.
Background technology
Polyamide (PA) is commonly called as nylon, is the engineering plastics with good mechanical properties and the excellent properties such as wear-resisting, anti-solvent, oil resistant, is widely used in industry-by-industry.But the shock strength of nylon is lower, has limited nylon resin to the application in the higher field of material performance requirement, particularly requires the occasion of high impact-resistant.Therefore, for adapting to the needs of industrial development, the impact that improves nylon is very important.At present, the Nylon In Toughening By Blending method mainly concentrate on by with other lactan or amino acid copolymerization, perhaps come toughness reinforcing with components such as rubber or elastomericss.Modification by copolymerization generally adopts the lactan of long carbochain as comonomer, changes the regularity of nylon molecular chain, reduces the degree of crystallinity of nylon, thereby causes shock strength to increase.This method of modifying need to begin reaction from polymer monomer, the processing condition more complicated, and also the residue small molecule monomer is difficult to remove, thus affect the performance of nylon.Thereby, in order to improve the toughness of nylon, the most frequently used method of modifying be with rubber or elastomerics as toughner, by with nylon blending, rubber or elastomerics are dispersed in the nylon matrix.When being subject to foreign impacts, rubber or elastomerics can absorbed energies, and produce Cavitated and surrender, and then transmit by the interface and to cause crazing and shear zone, a large amount of consumed energies, thus improve the nylon shock resistance.For example, ethylene-propylene rubber (EPR), ethylene-propylene-diene copolymer (EPDM), styrene-butadiene-styrene (SBS), SIS/SEBS (SEBS), ethene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA) etc. all have been used as the toughner of nylon.But, because the consistency of these toughner and nylon matrix is too poor, thereby needs to add compatilizer or improve consistency between rubber and the nylon, promotion rubber or the dispersion of elastomerics in nylon by modified rubber.Commonly used is the elastomerics of maleic anhydride graft, such as maleic anhydride grafted polyethylene (PE-g-MAH), maleic anhydride grafted ethene-1-octene etc.These methods all are at first will hang down molecular activity material chemistry to be reacted to the rubber that obtains containing reactive group on rubber or the elastomerics, and then with nylon blending two the step operations, the extruding pelletization of former process rubber particularly, because low molecular activity material proportion is lower, the relatively more difficult control of the percentage of grafting of reactive group, therefore all there is complex process in these methods, and energy consumption is large, the shortcoming of unstable product quality.
Summary of the invention
The object of the invention is to overcome defective of the prior art, nylon resin of a kind of toughened with silicon rubber modification and preparation method thereof is provided, described method increase-volume and toughness reinforcingly carry out synchronously, method is easy and simple to handle, prepared nylon resin has good mechanical property and good heat-resisting oil resistance.
The present invention is achieved by the following technical programs.
A kind of nylon resin of toughened with silicon rubber modification, the moiety of described nylon resin is as follows by mass parts:
The nylon resin of above-mentioned a kind of toughened with silicon rubber modification, wherein, the kind of described nylon is nylon 6, （Fen Mo/Ke Li） Nylon11 in powder/granular form, nylon 12 and nylon 66.
The nylon resin of above-mentioned a kind of toughened with silicon rubber modification, wherein, described polysiloxane is the polysiloxane that on average contains at least 2 vinyl on every siloxane chain.
The nylon resin of above-mentioned a kind of toughened with silicon rubber modification, wherein, described polysiloxane is methylvinyl-polysiloxane.
The nylon resin of above-mentioned a kind of toughened with silicon rubber modification, wherein, described compatilizer is amido silicon oil.
The nylon resin of above-mentioned a kind of toughened with silicon rubber modification, wherein, described linking agent is the containing hydrogen silicone oil that per molecule contains 2 si-h bonds at least.
The nylon resin of above-mentioned a kind of toughened with silicon rubber modification, wherein, described catalyzer is the platinum complex catalyst.
The nylon resin of above-mentioned a kind of toughened with silicon rubber modification, wherein, described catalyzer is a kind of in Platinic chloride-Virahol, Platinic chloride-tetramethyl divinyl disiloxane or the Platinic chloride-diethyl phthalate.
The preparation method of the nylon resin of above-mentioned a kind of toughened with silicon rubber modification, preparation process is as follows: at first nylon, polysiloxane and compatilizer are joined and carry out melting mixing in Banbury mixer or the forcing machine, blending temperature 180-230 ℃, 5-10 minute blend time, and then add the polysiloxane dynamic vulcanization that linking agent and catalyzer make disperse phase, the nylon resin of the toughened with silicon rubber modification that obtains vulcanizing, the temperature of dynamic vulcanization are 180-230 ℃.
Polysiloxane and nylon are inconsistent two base polymers of thermodynamics, in order to obtain satisfied blending and modifying effect, the present invention adopts amido silicon oil as compatilizer, when with the nylon melt blending, amido functional group in the compatilizer can with the carboxyl reaction realization response increase-volume of nylon molecular end, reduce the interfacial tension between two base polymers, promote the dispersion of polysiloxane in nylon, the blend performance is improved.Utilize the carboxyl original position of amino in the compatilizer and nylon to generate compatilizer, improve the degree of scatter of polysiloxane in nylon, and then add containing hydrogen silicone oil linking agent and platinum complex catalyst and make disperse phase polysiloxane dynamic vulcanization in the nylon matrix, the nylon resin that the silicon rubber that obtains vulcanizing is particle-filled, thereby the toughened with silicon rubber of realization nylon.
Preparation method's increase-volume of toughened with silicon rubber modification of nylon resin of the present invention and toughness reinforcingly carry out synchronously can by time processing with silicon rubber Uniform Dispersion and with the silicon rubber dynamic vulcanization of disperse phase in nylon, realize the toughness reinforcing of nylon.Complete processing of the present invention is simple, compares with the rubber of other type or the method for elastomer toughened nylon, and prepared nylon has good heat-resisting oil resistance and the excellent properties such as shock-resistant, can be used for automobile, building and the field such as electric.
Embodiment
In following examples, melting mixing and dynamic vulcanization all carry out in Banbury mixer.
The test mode that adopts:
Elongation test: press the test of GB1040-2006 method, rate of extension is 5mm/min.
Notched Izod impact strength: press GB1843-2008 method test socle girder notched Izod impact strength, select the 1J pendulum.
Shore hardness: press the test of ASTM D1415 method.
Embodiment 1
With 100 parts nylon 6, the compatilizer amido silicon oil of 25 parts methylvinyl-polysiloxane and 6 parts joins and carries out melting mixing in the Banbury mixer, after mixing 10 minutes under 230 ℃, add again 1.2 parts of linking agent containing hydrogen silicone oils and 0.012 part of platinum complex catalyst Platinic chloride-tetramethyl divinyl disiloxane, after carrying out dynamic vulcanization under 230 ℃, take out sample, be injection molded into batten test products performance.
Comparative example 1: with 25 parts methylvinyl-polysiloxane, the Platinic chloride of 1.2 parts containing hydrogen silicone oil and 0.012 part-tetramethyl divinyl disiloxane joins in the Banbury mixer after mixing, at 230 ℃ of lower dynamic vulcanizations, the silicon rubber that obtains vulcanizing; Then the silicon rubber of 25 parts of these sulfurations, 100 parts of nylon 6 and 6 parts of amido silicon oils are joined in the Banbury mixer, under 230 ℃, mixed 10 minutes, take out sample, be injection molded into batten test products performance.
Comparative example 2: with 100 parts nylon 6,25 parts methylvinyl-polysiloxane joins in the Banbury mixer, after mixing 10 minutes under 230 ℃, add again 1.2 parts containing hydrogen silicone oil and Platinic chloride-tetramethyl divinyl disiloxane of 0.012 part, after carrying out dynamic vulcanization under 230 ℃, take out sample, be injection molded into batten test products performance.
Table 1 embodiment 1 and comparative example 1, comparative example 2 comparative test result
As can be seen from Table 1, polysiloxane elder generation dynamic vulcanization is mixed the nylon resin mechanical property that (comparative example 1) obtain again with nylon relatively poor, with polysiloxane with after nylon mixes again dynamic vulcanization (embodiment 1) can obviously improve the mechanical property of nylon resin.Under the condition of not adding compatilizer (comparative example 2), the disperse phase polysiloxane disperses relatively poor in the nylon-6 matrix body, causes the mechanical property of nylon resin relatively poor.
Embodiment 2
With 100 parts nylon 6, the amido silicon oil of 25 parts methylvinyl-polysiloxane and 2.5 parts joins and carries out melting mixing in the Banbury mixer, after mixing 5 minutes under 230 ℃, add again 0.8 part containing hydrogen silicone oil and Platinic chloride-tetramethyl divinyl disiloxane of 0.008 part, after carrying out dynamic vulcanization under 230 ℃, take out sample, be injection molded into batten test products performance.
Embodiment 3
With 100 parts nylon 6, the amido silicon oil of 25 parts methylvinyl-polysiloxane and 2.5 parts joins and carries out melting mixing in the Banbury mixer, after mixing 10 minutes under 220 ℃, add again 5 parts containing hydrogen silicone oil and Platinic chloride-tetramethyl divinyl disiloxane of 0.1 part, after carrying out dynamic vulcanization under 220 ℃, take out sample, be injection molded into batten test products performance.With embodiment 1 and embodiment 2 contrasts, can find out that although linking agent can improve the degree of crosslinking of silicon rubber and improve impelling strength, excessive adding but can cause the decline of shock strength.
Embodiment 4
With 100 parts nylon 6, the amido silicon oil of 10 parts methylvinyl-polysiloxane and 1 part joins and carries out melting mixing in the Banbury mixer, after mixing 10 minutes under 230 ℃, add again 0.5 part containing hydrogen silicone oil and Platinic chloride-tetramethyl divinyl disiloxane of 0.005 part, after carrying out dynamic vulcanization under 230 ℃, take out sample, be injection molded into batten test products performance.
Embodiment 5
With 100 parts nylon 6, the amido silicon oil of 55 parts methylvinyl-polysiloxane and 8 parts joins and carries out melting mixing in the Banbury mixer, after mixing 8 minutes under 225 ℃, add again 1.5 parts containing hydrogen silicone oil and Platinic chloride-tetramethyl divinyl disiloxane of 0.015 part, after carrying out dynamic vulcanization under 225 ℃, take out sample, be injection molded into batten test products performance.
Embodiment 6
With 100 parts nylon 12, the amido silicon oil of 25 parts methylvinyl-polysiloxane and 5 parts joins and carries out melting mixing in the Banbury mixer, after mixing 10 minutes under 180 ℃, add again 1 part containing hydrogen silicone oil and Platinic chloride-tetramethyl divinyl disiloxane of 0.01 part, after carrying out dynamic vulcanization under 180 ℃, take out sample, be injection molded into batten test products performance.
Table 2 embodiment 2-6 experimental performance data
Claims (9)
1. the nylon resin of a toughened with silicon rubber modification is characterized in that, the moiety of described nylon resin is as follows by mass parts:
2. the nylon resin of a kind of toughened with silicon rubber modification as claimed in claim 1 is characterized in that, the kind of described nylon is nylon 6, （Fen Mo/Ke Li） Nylon11 in powder/granular form, nylon 12 and nylon 66.
3. the nylon resin of a kind of toughened with silicon rubber modification as claimed in claim 1 is characterized in that, described polysiloxane is the polysiloxane that on average contains at least 2 vinyl on every siloxane chain.
4. the nylon resin of a kind of toughened with silicon rubber modification as claimed in claim 3 is characterized in that, described polysiloxane is methylvinyl-polysiloxane.
5. the nylon resin of a kind of toughened with silicon rubber modification as claimed in claim 1 is characterized in that, described compatilizer is amido silicon oil.
6. the nylon resin of a kind of toughened with silicon rubber modification as claimed in claim 1 is characterized in that, described linking agent is the containing hydrogen silicone oil that per molecule contains 2 si-h bonds at least.
7. the nylon resin of a kind of toughened with silicon rubber modification as claimed in claim 1 is characterized in that, described catalyzer is the platinum complex catalyst.
8. the nylon resin of a kind of toughened with silicon rubber modification as claimed in claim 7 is characterized in that, described catalyzer is a kind of in Platinic chloride-Virahol, Platinic chloride-tetramethyl divinyl disiloxane or the Platinic chloride-diethyl phthalate.
9. the preparation method of the nylon resin of a kind of toughened with silicon rubber modification as claimed in claim 1, it is characterized in that, preparation process is as follows: at first nylon, polysiloxane and compatilizer are joined and carry out melting mixing in Banbury mixer or the forcing machine, blending temperature 180-230 ℃, 5-10 minute blend time, and then add the polysiloxane dynamic vulcanization that linking agent and catalyzer make disperse phase, and the nylon resin of the toughened with silicon rubber modification that obtains vulcanizing, the temperature of dynamic vulcanization is 180-230 ℃.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103725013A (en) * | 2013-12-16 | 2014-04-16 | 芜湖万润机械有限责任公司 | Nylon mixed silica gel material for automobile damping |
| CN105331102A (en) * | 2015-12-15 | 2016-02-17 | 上海杰事杰新材料(集团)股份有限公司 | Toughened nylon 66 material and preparation method and application thereof |
| CN107057067A (en) * | 2016-12-30 | 2017-08-18 | 浙江大学 | Three block response type compatilizer and preparation method thereof |
| CN108219447A (en) * | 2018-01-19 | 2018-06-29 | 四川大学 | A kind of preparation method of dynamic vulcanization polyamide/silicon rubber thermoplastic elastomer |
| CN109735103A (en) * | 2019-01-14 | 2019-05-10 | 浙江新力新材料股份有限公司 | It soaks resistance to precipitation flame retardant polyamide composite material and preparation method thereof |
| CN109989128A (en) * | 2019-03-11 | 2019-07-09 | 东华大学 | The nylon fiber and preparation method thereof that skin-friction coefficient is low and hydrophobicity improves |
| CN115368057A (en) * | 2022-08-18 | 2022-11-22 | 北京中天路业科技有限公司 | Direct-vat additive for asphalt mixture and preparation method thereof |
Citations (1)
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| CN1429253A (en) * | 2000-07-26 | 2003-07-09 | 陶氏康宁公司 | Thermoplastic silicone elastomers from compatibilized polyamide resins |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1429253A (en) * | 2000-07-26 | 2003-07-09 | 陶氏康宁公司 | Thermoplastic silicone elastomers from compatibilized polyamide resins |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103725013A (en) * | 2013-12-16 | 2014-04-16 | 芜湖万润机械有限责任公司 | Nylon mixed silica gel material for automobile damping |
| CN105331102A (en) * | 2015-12-15 | 2016-02-17 | 上海杰事杰新材料(集团)股份有限公司 | Toughened nylon 66 material and preparation method and application thereof |
| CN105331102B (en) * | 2015-12-15 | 2018-01-16 | 上海杰事杰新材料(集团)股份有限公司 | Toughed nylon66 material and its preparation method and application |
| CN107057067A (en) * | 2016-12-30 | 2017-08-18 | 浙江大学 | Three block response type compatilizer and preparation method thereof |
| CN107057067B (en) * | 2016-12-30 | 2020-04-24 | 浙江大学 | Triblock reactive compatilizer and preparation method thereof |
| CN108219447A (en) * | 2018-01-19 | 2018-06-29 | 四川大学 | A kind of preparation method of dynamic vulcanization polyamide/silicon rubber thermoplastic elastomer |
| CN109735103A (en) * | 2019-01-14 | 2019-05-10 | 浙江新力新材料股份有限公司 | It soaks resistance to precipitation flame retardant polyamide composite material and preparation method thereof |
| CN109735103B (en) * | 2019-01-14 | 2021-12-21 | 浙江新力新材料股份有限公司 | Precipitation-resistant halogen-free flame-retardant polyamide composite material soaked in water and preparation method thereof |
| CN109989128A (en) * | 2019-03-11 | 2019-07-09 | 东华大学 | The nylon fiber and preparation method thereof that skin-friction coefficient is low and hydrophobicity improves |
| CN109989128B (en) * | 2019-03-11 | 2020-06-02 | 东华大学 | Nylon fiber with low surface friction coefficient and improved hydrophobicity and preparation method thereof |
| CN115368057A (en) * | 2022-08-18 | 2022-11-22 | 北京中天路业科技有限公司 | Direct-vat additive for asphalt mixture and preparation method thereof |
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| CN102964822B (en) | 2014-04-09 |
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Owner name: JIANGSU TIANCHEN NEW MATERIAL CO., LTD. Free format text: FORMER NAME: JIANGSU TIANCHEN SILICON MATERIALS CO., LTD. |
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Address after: Yangzhong City Development Zone, Jiangsu city of Zhenjiang province 212211 Hong Kong Road No. 568 Patentee after: JIANGSU TIANCHEN NEW MATERIALS CO., LTD. Address before: Yangzhong City Development Zone, Jiangsu city of Zhenjiang province 212211 Hong Kong Road No. 568 Patentee before: JIANGSU TIANCHEN NEW MATERIALS CO., LTD. |