CN1058024C - Nylon 6 resin with excellent tension property and shock resistance and its preparation - Google Patents
Nylon 6 resin with excellent tension property and shock resistance and its preparation Download PDFInfo
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- CN1058024C CN1058024C CN97108021A CN97108021A CN1058024C CN 1058024 C CN1058024 C CN 1058024C CN 97108021 A CN97108021 A CN 97108021A CN 97108021 A CN97108021 A CN 97108021A CN 1058024 C CN1058024 C CN 1058024C
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Abstract
The present invention discloses nylon 6 resin with excellent tension property and shock resistance, and a preparation method thereof. Tenuous silicon dioxide granules and amino silane compounds with a general formula of NH2 Rm (ORn) 3 Si can be used as a coupling agent, the coupling agent and a caprolactam monomer can be prepared to mother liquid first, the mother liquid and the caprolactam raw material can be mixed in the proportion of 1: 20 to 1: 30 by weight, and then modified nylon 6 resin can be obtained by polymerizing, discharging, pelleting, extracting and drying. The modified nylon 6 resin can solve the problems of poor tensility, poor impact resistance, etc. of the nylon 6 resin, which has the advantages of easy production, low cost, high mechanical strength of resin, etc. The elongation at break and the notch impact strength of the resin can reach more than 250 percent and 25 kj/m<2>, and the present invention can be used for manufacturing biaxial stretching films and high tenacity engineering plastics.
Description
The present invention relates to a kind of Nylon 6 and preparation method thereof with excellent tension property and shock resistance.
In the prior art, nylon 6 is a kind of broad-spectrum macromolecular materials, but the elongation at break of general Nylon 6 is about 30%, and notched Izod impact strength is 6KJ/m
2About (see domestic PA6 product standard HG-868-76, testing method adopts GB-1040-79), for being used as higher film (as biaxially oriented film) and the higher engineering plastics of toughness reguirements of draw ratio, its tensile property and shock resistance can meet the demands.In order to improve the tensility energy and the shock resistance of nylon 6, need nylon 6 is carried out physics or chemical modification, physical modification method commonly used is to add a certain amount of properties-correcting agent to carry out melt blending in twin screw extruder.At " engineering plastics application " (Liu Chunxiao volume, 1996, Vol.24 (1), P34) report in: make compatilizer with maleic anhydride inoculated polypropylene, add 10% above polypropylene melting mixing in twin screw, the nylon 6 alloy elongation at break of preparing is 250%, notched Izod impact strength 28KJ/m
2But this method need be carried out secondary granulation, and needs the special-purpose compatilizer of preparation, complex process, and cost is higher, and product can only be used as engineering plastics, should not be used as film." engineering plastics application " (compile square Hailin, 1996, Vol.24 (2), P15) in report: make the properties-correcting agent of PA6 with rare-earth mineral, add rare earth melting mixing in twin screw of 15%, the notched Izod impact strength of the modified Pa 6 of preparation is from 5.5KJ/m
2Bring up to 8.5KJ/m
2, this method needs secondary granulation equally, and the notched Izod impact strength of product improves seldom.The common chemical method of modifying is to introduce second kind of nylon monomer (as nylon salt etc.) to carry out copolycondensation in polymerization process, and the elongation at break of the copolymer polyamide resin of preparation and notched Izod impact strength can improve greatly than pure PA6.At " polyamide resin handbook " (P385, (day), volume was repaiied in the Feitian, and Shi Zupei etc. translate, Sinopec press) the middle copolymer nylon CM6041 (nylon 6/66 copolymer of Dong Li company) that reports, its elongation at break is greater than 200%, and notched Izod impact strength is greater than 30KJ/m
2, but this method has relatively high expectations to polymerization technique, and general nylon 6/poly attaches together to put and can not reach requirement.
The objective of the invention is to: provide a kind of attaching together to put at existing nylon 6/poly, by adding a small amount of additive, in polymerization process, prepare Nylon 6 with good stretchiness and shock resistance and preparation method thereof, need not add auxiliary agent and in screw rod, carry out secondary granulation, preparation technology is simple, cost is lower, and product stretchiness and good impact resistance are particularly useful for making nylon 6 biaxially oriented films and high-toughness engineering plastic.
The objective of the invention is to realize by the following technical solutions: preparation earlier contains the hexanolactam mother liquor of amorphous silica and coupling agent, again mother liquor is added to and carries out polymerization in the caprolactam monomer, detailed process mainly comprises: (1) preparation mother liquor, use the white rouge pellet, and use general formula to be NH
2Rm (ORn)
3(R is CH to the amino containing silane compounds of Si in the formula
2N is 1～3 positive integer, m is another any positive integer of 2～18) one or more make coupling agent, in silicon-dioxide: coupling agent: the ratio of hexanolactam=1: 0.05～0.3: 10～50 (weight), coupling agent and amorphous silica be added in 80～100 ℃ the hexanolactam molten monomer, insulated and stirred promptly gets mother liquor half an hour; (2) polymerization, it by the weight ratio of mother liquor and caprolactam monomer raw material 1: 20～30 mixed, under the pressure of 250～270 ℃ temperature and 0.1～0.5MPa, reacted 1～2 hour, and under 250～270 ℃, normal pressure or negative pressure, reacted 2～4 hours after the step-down; (3) reaction finishes back discharging, pelletizing, and section with 90～100 ℃ water hot extraction 6～12 hours, is 100～120 ℃ in temperature again, vacuumized under the condition drying 12 hours, prepares the Nylon 6 that contains the white rouge additive.
The present invention's technical scheme preferably can be: the coupling agent of preparation mother liquor adopts silane compound, preferably uses general formula to be NH
2Rm (ORn)
3The amino containing silane compounds of Si is as amine propyl group three (oxyethyl group) silane, amine octyl group trimethoxy silane, amine osmanthus base three (propoxy-) silane, amine propyl group three (propoxy-) silane and amine octadecyl three (oxyethyl group) silane etc.In the process of preparation nylon 6, coupling agent can be aforesaid compound a kind of, two kinds or multiple mixing use wherein, all can play same effect.Preferably unformed subparticle of used silicon-dioxide such as particle size range are the silicon-dioxide of 10～100mm, silicon-dioxide is a kind of additive of main toughening effect, coupling agent then plays the effect that improves consistency between silicon-dioxide and the nylon, is a kind of surface-modifying agent of silicon dioxide microparticle.In the process of preparation mother liquor, silicon-dioxide: coupling agent: hexanolactam (weight ratio) is generally 1: 0.05～0.3: 10～50, the consumption of silicon-dioxide is crossed and is difficult at most disperse in system, the coupling agent consumption is wanted suitably, consumption too much not only can increase cost, and the physical and mechanical properties of nylon 6 products such as hardness and tensile strength are decreased.
The present invention's technical scheme preferably also can be: in the process of preparation Nylon 6, white rouge pellet add-on is 0.1%～0.3% (weight) of system total amount (or amount of resin), can reach optimum toughening effect like this, and silicon-dioxide is scattered, production cost is low.Obviously, the consumption of silicon-dioxide is crossed the low toughening effect that then product is not had expection, influences the tensile property and the shock resistance of product; There is no need to add too much silicon-dioxide, its consumption too much can cause its difficulties in dispersion in system, product performance instability.
The present invention's technical scheme preferably can also be: in the process of preparation Nylon 6, the add-on of coupling agent is 10%～20% (weight) of amorphous silica amount, in this amount ranges, can improve the consistency between nylon 6 and the silicon-dioxide preferably, be beneficial to the toughening effect that improves silicon-dioxide, improve the physical and mechanical properties of resin.
Compared with prior art, the present invention has following tangible advantage:
1, adopts preparation mother liquor method earlier, silicon-dioxide and coupling agent joined together carry out polymerization in the system, can make coupling agent concentrate on silica sphere earlier, can save the surface treatment procedure of silicon-dioxide, and preventing the cohesion of silicon-dioxide, direct preparation modified resin in polymerization process has saved resin modified screw rod secondary granulation operation commonly used, thereby manufacturing process is simple, and cost is low.
2, adopt the amino containing silane compounds to make coupling agent, affinity is preferably arranged between amido and nylon, silane and silicon-dioxide have affinity preferably, thereby can improve consistency between nylon and the silicon-dioxide preferably, the white rouge pellet can significantly improve the tensile property and the shock resistance of nylon 6, the Nylon 6 elongation at break can reach more than 250%, and notched Izod impact strength can reach 25KJ/m
2More than, twice index improves respectively more than 8 times and 4 times than general nylon 6 resins, thereby good product quality, and product is applicable to preparation biaxially oriented film and high-toughness engineering plastic, has widened the Application Areas of Nylon 6.
Below the present invention is described in further detail by specific embodiment:
Embodiment 1: take by weighing hexanolactam 100 grams, in beaker, be heated to 80～100 ℃, treat to add 0.8 donaxine propyl group three (oxyethyl group) silane and the fine amorphous silica of 4 grams after the fusion, insulated and stirred promptly makes mother liquor after 30 minutes, this mother liquor and 1900 lactan of restraining oneself is added in the reactor that volume is 5L together, reaction is 1.5 hours under the pressure of 250～270 ℃ temperature and 0.1～0.5MPa, after the step-down, reaction is 3 hours under 250～270 ℃ and normal pressure, discharging, pelletizing, to cut into slices with 90～100 ℃ of water hot extractions 6 hours, again at 120 ℃, vacuumized under the condition dry 12 hours, and promptly got modification of nylon 6 resins.Adopt national standard method (GB-1040-79 and GB-1043-79) to survey the elongation at break and the notched Izod impact strength of this Nylon 6, its value is respectively 268% and 30.2KJ/m
2
In the present embodiment, SiO
2Weight is 0.2% of weight resin, and the weight of coupling agent is 0.04% of weight resin, and the add-on of coupling agent is 20% of a silica weight.
Embodiment 2～6: step and method are with embodiment 1, and technology controlling and process is with embodiment 1, and the add-on of its silicon-dioxide and coupling agent, corresponding physical and mechanical properties (testing standard is the same) see table 1 for details.
Table 1 Nylon 6 raw material is formed and the physical and mechanical properties table
Annotate: 1. being amine propyl group three (oxyethyl group) silane in the table, 2. is amine octyl group trimethoxy silane, 3. is amine osmanthus base three (propoxy-) silane,
| Embodiment | Mother liquor is formed | Polymerization amount of monomer (gram) | Content in the system | Physical and mechanical properties | |||||
| SiO 2Amount (gram) | Coupling agent | Coupling dosage (gram) | Amount of monomer (gram) | SiO 2 (％) | Coupling agent (%) | Elongation at break (%) | Notched Izod impact strength (KJ/m 2) | ||
| 1 | 4.0 | ① | 0.8 | 100 | 1900 | 0.2 | 0.04 | 268 | 30.2 |
| 2 | 6.0 | ② | 0.3 | 100 | 1900 | 0.3 | 0.015 | 256 | 28.0 |
| 3 | 10.0 | ④ | 0.92 | 100 | 1900 | 0.5 | 0.05 | 252 | 26.0 |
| 4 | 1.0 | ①，③ | 0.2，0.1 | 100 | 1900 | 0.05 | 0.015 | 302 | 29.8 |
| 5 | 2.0 | ②，④ | 0.1，0.3 | 100 | 1900 | 0.1 | 0.02 | 282 | 28.6 |
| 6 | 4.0 | ①，③，⑤ | 0.3，0.2，0.3 | 100 | 1900 | 0.2 | 0.04 | 296 | 32.3 |
4. being amine propyl group three (propoxy-) silane, 5. is amine octadecyl three (oxyethyl group) silane.
Claims (3)
1, a kind of preparation method with excellent tension property and shock resistance Nylon 6, comprise monomer preparation, polymerization, pelletizing, extraction and drying process, it is characterized in that: preparation earlier contains the hexanolactam mother liquor of amorphous silica and coupling agent, mother liquor is added to again and carries out polymerization in the caprolactam monomer, detailed process mainly comprises:
(1) the preparation mother liquor uses the white rouge pellet, and uses general formula to be NH
2Rm (ORn)
3(R is CH to the amino containing silane compounds of Si in the formula
2N is 1～3 positive integer, m is another any positive integer of 2～18) one or more make coupling agent, press silicon-dioxide: coupling agent: the part by weight of hexanolactam=1: 0.05～0.3: 10～50, coupling agent and amorphous silica be added in 80～100 ℃ the hexanolactam molten monomer, insulated and stirred promptly gets mother liquor half an hour, then
(2) polymerization, it by the weight ratio of mother liquor and caprolactam monomer raw material 1: 20～30 mixed, under the pressure of 250～270 ℃ temperature and 0.1～0.5MPa, reacted 1～2 hour, and under 250～270 ℃, normal pressure or negative pressure, reacted 2～4 hours after the step-down, then
(3) discharging, pelletizing, extraction, drying.
2, the preparation method of Nylon 6 according to claim 1 is characterized in that white rouge pellet add-on is 0.1%～0.3% of system gross weight or a weight resin.
3, the preparation method of Nylon 6 according to claim 1, the add-on that it is characterized in that coupling agent is 10%～20% of a silica weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97108021A CN1058024C (en) | 1997-04-11 | 1997-04-11 | Nylon 6 resin with excellent tension property and shock resistance and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97108021A CN1058024C (en) | 1997-04-11 | 1997-04-11 | Nylon 6 resin with excellent tension property and shock resistance and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1166508A CN1166508A (en) | 1997-12-03 |
| CN1058024C true CN1058024C (en) | 2000-11-01 |
Family
ID=5170054
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97108021A Expired - Fee Related CN1058024C (en) | 1997-04-11 | 1997-04-11 | Nylon 6 resin with excellent tension property and shock resistance and its preparation |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102863903A (en) * | 2012-10-16 | 2013-01-09 | 河南工业大学 | Monomer casting (MC) nylon polishing abrasive grain used in roller polishing machine and preparation method of MC nylon polishing abrasive grain |
| CN103992474B (en) * | 2014-06-11 | 2016-03-30 | 南方医科大学 | A kind of preparation method of ultrabranching polyamide modified organic silicone resin and the standby coating of this resin-made |
| CN107915987B (en) * | 2016-10-11 | 2021-01-05 | 中国石油化工股份有限公司 | Combined raw material for preparing polyamide film and preparation method thereof |
| CN116003780A (en) * | 2023-01-09 | 2023-04-25 | 华润化学材料科技股份有限公司 | Nylon engineering plastic and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1451726A (en) * | 1973-11-16 | 1976-10-06 | Merck Patent Gmbh | Preparation of organic-modified silicon dioxides |
| GB1483540A (en) * | 1973-12-10 | 1977-08-24 | Bayer Ag | Process for the production of moulded polyamide products |
| JPS5369297A (en) * | 1976-12-02 | 1978-06-20 | Starlite Ind | Manufacture of polyimide compound |
| JPS5922922A (en) * | 1982-07-28 | 1984-02-06 | Mitsuboshi Belting Ltd | Manufacture of monomer-cast nylon containing filler |
-
1997
- 1997-04-11 CN CN97108021A patent/CN1058024C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1451726A (en) * | 1973-11-16 | 1976-10-06 | Merck Patent Gmbh | Preparation of organic-modified silicon dioxides |
| GB1483540A (en) * | 1973-12-10 | 1977-08-24 | Bayer Ag | Process for the production of moulded polyamide products |
| JPS5369297A (en) * | 1976-12-02 | 1978-06-20 | Starlite Ind | Manufacture of polyimide compound |
| JPS5922922A (en) * | 1982-07-28 | 1984-02-06 | Mitsuboshi Belting Ltd | Manufacture of monomer-cast nylon containing filler |
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| Publication number | Publication date |
|---|---|
| CN1166508A (en) | 1997-12-03 |
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Inventor after: Xiong Yuanfan Inventor after: Shang Yong Inventor after: Wan Ping Inventor after: Wei Zhonghui Inventor after: Han Fei Inventor after: Cheng Yanting Inventor after: Liu Ying Inventor after: Cui Zhangyu Inventor before: Xiong Yuanfan Inventor before: Shang Yong Inventor before: Wan Ping Inventor before: Han Fei Inventor before: Cheng Yanting Inventor before: Liu Ying Inventor before: Cui Zhangyu |
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Free format text: CORRECT: INVENTOR; FROM: XIONG YUANFAN; SHANG YONG; WAN PING; HAN FEI; CHENG YANTING; LIU YING; CUIZHANGYU TO: XIONG YUANFAN; SHANG YONG; WAN PING; WEI ZHONGHUI; HAN FEI; CHENG YANTING; LIU YING; CUI ZHANGYU |
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Owner name: BALING PETROCHEMICAL CO., LTD., SINOPEC Free format text: FORMER OWNER: YUEYANG PETRO-CHEMICAL GENERAL PLANT, BALING PETRO-CHEMICAL CO Effective date: 20030124 |
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Effective date of registration: 20030124 Address after: Hunan province Yueyang city Yunxi District of Baling Petrochemical Limited liability company technology development department Patentee after: Baling Petrochemical Co., Ltd., SINOPEC Address before: Yunxi town Yueyang city Hunan Province Patentee before: Yueyang Petrochemical general Plant, Baling Petrochemical Corp. |
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