CN105086432A - High-viscosity nylon 6 and preparation method thereof - Google Patents
High-viscosity nylon 6 and preparation method thereof Download PDFInfo
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- CN105086432A CN105086432A CN201510530152.7A CN201510530152A CN105086432A CN 105086432 A CN105086432 A CN 105086432A CN 201510530152 A CN201510530152 A CN 201510530152A CN 105086432 A CN105086432 A CN 105086432A
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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
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
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- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/04—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to rubbers
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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
- 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 Kinetics & Catalysis (AREA)
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Abstract
The invention provides high-viscosity nylon 6, made from nylon 6, low temperature resistant toughener, wear-resistant agent, antioxidant, black masterbatch, and chain extender according to a reasonable ratio. The high-viscosity nylon 6 is high in molecular weight, high in viscosity and good in mechanical property. The invention further provides a preparation method of the high-viscosity nylon 6. The preparation method includes sequential steps of blending, mixing, drying and the like; the preparation method is simple and high in response speed; the defect that high viscosity of materials in later period of reaction causes difficulty of stirring and byproduct spreading is overcome. The preparation method is applicable to the preparation of the high-viscosity nylon 6 and is further applicable to processing and application of spring guards for heavy-duty trucks.
Description
Technical field
The invention belongs to Polymer Synthesizing field, relate to a kind of nylon, specifically a kind of high sticky nylon 6 and preparation method thereof.
Background technology
Nylon (PA) is the good engineering plastics of a kind of over-all properties, is widely used in the every field such as automotive industry, electrical industry, material of construction, mechanical part, medicine equipment and daily necessities.Because it has good barrier to the organic solvent such as pharmaceutical chemicals, oils, the demand of container prepared by PA increases greatly.Along with the development of economic globalization process, China's automobile, electronic apparatus, communication, mechanical industry are also in develop rapidly, increasing to the demand of nylon, and also more and more higher to the requirement of its performance, kind, nylon has become the indispensable structured materials of industry such as automobile, machinery, electrical equipment communication, aerospace, national defence, packaging.
At present, the molecular weight (being about less than 20,000) of the PA that general polymerization method obtains and melt viscosity low, direct blow molding is difficult to when preparing hollow container, and as the PA that engineering plastics are applied, higher to the requirement of its molecular weight, therefore improve the viscosity of PA, make it have the focus that higher molecular weight becomes research at present.
The nylon of high molecular has viscosity higher, and full-bodied nylon has excellent physical and mechanical properties, and the height that heavy goods vehicles spring guard uses glues the nylon 6 material higher molecular weight of needs and melt viscosity.Existing height glues nylon 6, and to there is rigidity high, and the shortcomings such as low temperature embrittlement, can not meet the performance requriements of spring guard material.The method of current production high visocity nylon, mainly through extending melt phase polycondensation, extending the time of solid state polymerization, to reach the object of chain extension thickening.But it is high to there is energy consumption in the prolongation melt phase polycondensation time, the deficiency that product high temperature is easily degraded; And the speed of solid-phase polymerization is slow, can cause consuming time longer, scale operation needs special equipment in addition, virtually just adds production cost.In addition, apply existing formula and use above-mentioned two kinds of methods to produce high sticky nylon 6, certain difficulty is there is in reality, namely large in the viscosity of the later stage material of reaction, stir and diffusion difficulty, can aggravate the generation of by product, the content of end group increases, and causes quality product decline, mechanical property reduction.
Summary of the invention
The technical problem to be solved in the present invention, be to provide a kind of high sticky nylon 6, its reasonable raw material proportioning, this kind high sticky nylon 6 molecular weight is high, viscosity large, good mechanical performance;
Another object of the present invention, be to provide the preparation method of above-mentioned a kind of high sticky nylon 6, this preparation method is simple, and reaction is fast, the reaction later stage material viscosity that can overcome existing for prior art causes comparatively greatly the defect of stirring and by product diffusion difficulty, the product good mechanical property of preparation.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
A kind of high sticky nylon 6, the raw material making its effective constituent comprises according to weight parts:
Nylon 679-86 part,
Low temperature resistant toughner 10-15 part,
Anti-wear agent 2-4 part,
Oxidation inhibitor 0.3-0.5 part,
Black masterbatch 0.3-1 part,
Chainextender 0.5-1.5 part.
Limit as one of the present invention:
The relative viscosity of described nylon 6 is 2.8Pas.
In preparing product process, if the relative viscosity of nylon 6 is greater than 2.8Pas, then can cause during preparation material adhesion occurs, preparation difficulty increases, and the mechanical property of the finished product and wear resisting property low; If the relative viscosity of nylon 6 is less than 2.8Pas, then the finished product prepared are difficult to meet material indehiscent requirement at low temperature-40 DEG C;
Limit as another kind of the present invention:
Described low temperature resistant toughner is weight proportion is the ethylene propylene rubber of 1:2.3-4 and the mixture of grafting terpolymer EP rubber.
Compared with traditional toughner, the toughner that the present invention uses and PA6 have good consistency, and the batching of toughner is reasonable, can increase toughness of products, not affect other performance of material, improve successful.
Limit as of the present invention the third:
Described anti-wear agent is weight proportion is the tetrafluoroethylene of 1:0.6-1.5 and the mixture of molybdenumdisulphide.
As the 4th kind of restriction of the present invention:
Three (2.4-di-tert-butyl-phenyl) phosphorous acid ester, four [β-(3 of described oxidation inhibitor to be weight proportion be 1:1:2; 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and N; the mixture of N'-pair-(3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine.
The present invention also has a kind of restriction, the response type master batch that nylon chainextender is is carrier with nylon 6, and model is M-1251, can buy obtain from German Brueggemann chemical company;
Chainextender is the key assistant of material thickening, and the consumption of chainextender exists optimum range, insufficient by linked reaction during quantity not sufficient, end capping aggravation when consumption is excessive.The response type master batch Heat stability is good being at processing temperatures carrier with nylon 6, and can with the end group rapid reaction of polymkeric substance, reach the requirement of reactive extrursion, products obtained therefrom is even, and viscosity is large.
Present invention also offers the preparation method of above-mentioned a kind of high sticky nylon 6, it carries out according to following sequence of steps:
(1) mix
All raw materials and reaction mass are placed in mixing machine, make them mix, obtain A;
(2) mixing
Added by A in screw extrusion press, melting mixing at 230-260 DEG C, mixing 2-3min, extruding pelletization, obtains B;
The viscosity of mixing temperature on the finished product has important impact, and when temperature is lower than 230 DEG C, chain extending reaction speed is low, and the activity of the active group of PA6 is low, and the chain extending reaction time is long and the viscosity of the finished product is little; When temperature is higher than 260 DEG C, chainextender generation oxygenolysis, side reaction aggravates, and reduces the quality of the finished product;
Also there is important impact the mixing time on the viscosity of the finished product, and when the time is less than 2min, the system residence time is in an extruder few, causes chainextender and PA6 fully not to react, and the viscosity of the finished product reduces; When the time is greater than 3min, the system residence time is in an extruder longer, and more side reaction can occur, and reduces the quality of the finished product;
(3) dry
B is placed in drying baker dry, obtains target product, be i.e. a kind of high sticky nylon 6.
Restriction as to above-mentioned preparation method:
1. the rotating speed of described mixing machine is 200-500rpm;
2. the engine speed of described screw extrusion press is 200-400rpm, and vacuum tightness is 0.03-0.06MPa;
Double-screw extruder screw rotating speed is directly related with the relative molecular mass of the sticky nylon 6 of product height with the polymerization time of material, screw speed is large, and then polymerization time is short, the corresponding decline of relative molecular mass of the sticky nylon 6 of product height simultaneously, the little then polymerization time of rotating speed is long, the corresponding increase of relative molecular mass of the sticky nylon 6 of product height simultaneously, but the by product that reaction system meeting stages of labor is more, when screw speed is at 200-400rpm, the relative viscosity of the sticky nylon 6 of products therefrom height is high, and energy normal running, polyreaction can be carried out smoothly;
Vacuum tightness has material impact to mixing process, and vacuum tightness is too low, and the small-molecule substance produced in reaction is not easily removed, and higher vacuum tightness then can cause the wasting of resources.
3. the temperature of described drying baker is 95-115 DEG C.
Owing to have employed above-mentioned technical scheme, compared with prior art, acquired technical progress is in the present invention:
Height provided by the invention glues nylon 6, the reasonable ratio of raw material, and the height of preparation glues the problem that nylon 6 solves low temperature embrittlement, and have higher rigid nature, wear resistance is improved, and physical strength is high, meets the requirement of spring guard processing and use properties.
Height provided by the invention glues the preparation method of nylon 6, and preparation process is simple, and reaction is fast, and the reaction later stage material viscosity overcome existing for prior art causes comparatively greatly the defect of stirring and by product diffusion difficulty, and the height of preparation glues nylon 6 good mechanical property.
The present invention is applicable to the high sticky nylon 6 of preparation, is applied to processing and the application of heavy goods vehicles spring guard further.
The present invention is described in further detail below in conjunction with specific embodiment.
The test method used in following embodiment if no special instructions, is ordinary method.
Material used in following embodiment, reagent etc., if no special instructions, all can obtain from commercial channel.
Embodiment
the preparation method of the high sticky nylon 6 of embodiment 1 one kinds
The present embodiment carries out according to following sequence of steps:
(11) mix
Be the nylon 6 of 2.8PaS by 80kg relative viscosity, the low temperature resistant toughner of 15kg (mixture for 3.75kg ethylene propylene rubber and 11.25kg grafting terpolymer EP rubber), 2.7kg anti-wear agent (mixture for 1.4kg tetrafluoroethylene and 1.3kg molybdenumdisulphide), 0.3kg oxidation inhibitor { is 0.075kg tri-(2.4-di-tert-butyl-phenyl) phosphorous acid ester, 0.075kg tetra-[β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, and 0.15kgN, N'-pair-(3-(3, 5-di-tert-butyl-hydroxy phenyl) propionyl) mixture of hexanediamine }, 1kg black masterbatch, with the 1kg response type master batch that is carrier with nylon 6, originate from German Brueggemann chemical company, model is M-1251, being placed in rotating speed is 200rpm mixing machine, A1 is obtained after mixing,
(12) mixing
A1 being added engine speed is 400rpm, and vacuum tightness is in the twin screw extruder of 0.06MPa, melting mixing at 255 DEG C, mixing 2.3min, and extruding pelletization, obtains B1;
(13) dry
B1 being placed in temperature is 100 DEG C of drying bakers, obtains a kind of height and glues nylon 6, be designated as the 1st kind high sticky nylon 6 after oven dry.
sticky nylon 6 of embodiment 2 ~ 6 height and preparation method thereof
Embodiment 2
~6 are respectively a kind of high sticky nylon 6(is designated as the 2nd kind ~ the 6th kind high sticky nylon 6 successively) and preparation method thereof, they are similar to embodiment 1 respectively, and difference is only that the technical parameter in the proportioning of raw material and preparation process is different, specifically sees the following form.
Table 1 technical parameter table
the performance test of the high sticky nylon 6 of embodiment 7 the 1st ~ 6th kind
The present embodiment is to embodiment 1
~the 1st ~ 6th kind high sticky nylon 6 prepared in 6, carried out measuring mechanical property, the means of test are means of testing of the prior art, are specially:
1) tensile strength
By GB/T1040 test, test speed: 50mm/min;
2) elongation at break
By GB/T1040 test, test speed: 50mm/min;
3) flexural strength
By GB/T9341 test, test speed: 2mm/min;
4) simply supported beam notched Izod impact strength
Test by GB/T1043;
5) low temperature simply supported beam notched Izod impact strength (-40 DEG C)
Test by GB/T1043;
6) shore D type hardness tester
Test by GB/T2411;
7) melting index MFR
Test by GB/T3682.
1st ~ as shown in the table to the test result of the 6th kind high sticky nylon 6 mechanical property.
The test result of sticky nylon 6 mechanical property of table 2 height
The mechanical property requirements of heavy-duty car spring guard to material is: flexural strength>=40MPa, tensile strength>=45MPa, low temperature simply supported beam notched Izod impact strength (-40 DEG C)>=6KJ/m
2, elongation at break>=40%, shore D type hardness tester>=80.
As seen from the above table, the mechanical property of each high sticky nylon 6 that the embodiment of the present invention 1 ~ 6 provides, all can meet the requirement as heavy-duty car spring guard.
the temperature and time of embodiment 8 mixing process glues the impact of nylon 6 product performance on height
In mixing process, chain extending reaction can be there is, temperature of reaction and the residence time are the principal elements affecting chain extension effect, the present embodiment is probed into the impact of the temperature and time in mixing process on the performance of the finished product, raw material and preparation method similar to embodiment 1, difference is only corresponding temperature and time parameter difference, and (that is: the temperature in table 3 is different from embodiment 1, and other parameter is with embodiment 1; Time in table 4 is different from embodiment 1, and other parameter is with embodiment 1), result is as table 3, table 4.
The different melting temperature of table 3 glues the performance impact of nylon 6 to height
As can be seen from the above table; when melting temperature is at 230-260 DEG C; every mechanical performance index of high sticky nylon 6 is better; when melting temperature is lower than 230 DEG C; the motion of reaction process Middle molecule is slower; within the limited time, chainextender fully can not react with the end carboxyl of PA6 or Amino End Group, and therefore end group concentration is high, and its limiting viscosity increase is also limited; Along with the raising chain extending reaction speed of temperature increases, the end group reaction rate accelerates of chainextender and PA6, the end group concentration of PA6 is low, limiting viscosity constantly increases, and be greater than the condition of 260 DEG C in temperature under, the degree of chainextender generation oxygenolysis wants large many, more chainextender is caused to lose efficacy, side reaction increases, the viscosity degradation of products made thereby.
The different mixing time of table 4 glues the performance impact of nylon 6 to height
As can be seen from the above table, when mixing time is at 2-3min, every mechanical performance index of high sticky nylon 6 is better, is conducive to the generation of chain extending reaction, the good product performance therefore prepared, and all can meets processing and the application of spring guard in this time range.
Embodiment 1 ~ 6 is only preferred embodiment of the present invention, be not the restriction of other form made for the present invention, any those skilled in the art may utilize above-mentioned technology contents to be changed or be modified as the Equivalent embodiments of equivalent variations as enlightenment.In every case be the technical spirit not departing from the claims in the present invention, to simple modification, equivalent variations and remodeling done by above embodiment, still belong to the scope of the claims in the present invention protection.
Claims (10)
1. one kind high sticky nylon 6,
it is characterized in thatthe raw material making its effective constituent comprises according to weight parts:
Nylon 679-86 part,
Low temperature resistant toughner 10-15 part,
Anti-wear agent 2-4 part,
Oxidation inhibitor 0.3-0.5 part,
Black masterbatch 0.3-1 part,
Chainextender 0.5-1.5 part.
2. a kind of high sticky nylon 6 according to claim 1,
it is characterized in that:the relative viscosity of described nylon 6 is 2.8Pas.
3. a kind of high sticky nylon 6 according to claim 1,
it is characterized in that:described low temperature resistant toughner is weight proportion is the ethylene propylene rubber of 1:2.3-4 and the mixture of grafting terpolymer EP rubber.
4. a kind of high sticky nylon 6 according to claim 1,
it is characterized in that:described anti-wear agent is weight proportion is the tetrafluoroethylene of 1:0.6-1.5 and the mixture of molybdenumdisulphide.
5. a kind of high sticky nylon 6 according to claim 1,
it is characterized in that:three (2.4-di-tert-butyl-phenyl) phosphorous acid ester, four [β-(3 of described oxidation inhibitor to be weight proportion be 1:1:2; 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and N; the mixture of N'-pair-(3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine.
6. according to the sticky nylon 6 of one height in claim 1-5 described in any one,
it is characterized in that:the response type master batch that nylon chainextender is is carrier with nylon 6.
7. as a preparation method for a kind of high sticky nylon 6 in claim 1-6 as described in any one,
it is characterized in thatit carries out according to following sequence of steps:
(1) mix
Using all raw materials as reaction mass, be placed in mixing machine, after mixing, obtain A;
(2) mixing
Added by A in screw extrusion press, melting mixing at 230-260 DEG C, mixing 2-3min, extruding pelletization, obtains B;
(3) dry
B is placed in drying baker dry, obtains target product, be i.e. a kind of high sticky nylon 6.
8. the preparation method of a kind of high sticky nylon 6 according to claim 7,
it is characterized in that:the rotating speed of described mixing machine is 200-500rpm.
9. the preparation method of a kind of high sticky nylon 6 according to claim 7,
it is characterized in that:the engine speed of described screw extrusion press is 200-400rpm, and vacuum tightness is 0.03-0.06MPa.
10. according to the preparation method of a kind of high sticky nylon 6 in claim 7-9 described in any one,
it is characterized in that:the temperature of described drying baker is 95-115 DEG C.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107400353A (en) * | 2017-06-30 | 2017-11-28 | 徐州腾飞工程塑料有限公司 | A kind of automobile noise reduction piece nylon material and preparation method thereof |
| CN112590345A (en) * | 2020-11-30 | 2021-04-02 | 厦门长塑实业有限公司 | High-strength biaxially oriented nylon film and preparation method thereof |
| CN114805794A (en) * | 2022-03-31 | 2022-07-29 | 金发科技股份有限公司 | Application of compound in improving molecular weight of nylon |
| CN114836027A (en) * | 2022-04-25 | 2022-08-02 | 宁波坚锋新材料有限公司 | High-viscosity recycled nylon recovered from fishing net wires and preparation method thereof |
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| CN102020842A (en) * | 2010-12-22 | 2011-04-20 | 东莞市意普万工程塑料有限公司 | Nylon composite material special for electric wire and cable jacket and preparation method thereof |
| CN102051043A (en) * | 2009-10-30 | 2011-05-11 | 上海金发科技发展有限公司 | High wear-resistant and cold-resistant toughened nylon composite material |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102051043A (en) * | 2009-10-30 | 2011-05-11 | 上海金发科技发展有限公司 | High wear-resistant and cold-resistant toughened nylon composite material |
| CN102020842A (en) * | 2010-12-22 | 2011-04-20 | 东莞市意普万工程塑料有限公司 | Nylon composite material special for electric wire and cable jacket and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107400353A (en) * | 2017-06-30 | 2017-11-28 | 徐州腾飞工程塑料有限公司 | A kind of automobile noise reduction piece nylon material and preparation method thereof |
| CN112590345A (en) * | 2020-11-30 | 2021-04-02 | 厦门长塑实业有限公司 | High-strength biaxially oriented nylon film and preparation method thereof |
| CN114805794A (en) * | 2022-03-31 | 2022-07-29 | 金发科技股份有限公司 | Application of compound in improving molecular weight of nylon |
| CN114805794B (en) * | 2022-03-31 | 2023-08-29 | 金发科技股份有限公司 | Application of compound in improving molecular weight of nylon |
| CN114836027A (en) * | 2022-04-25 | 2022-08-02 | 宁波坚锋新材料有限公司 | High-viscosity recycled nylon recovered from fishing net wires and preparation method thereof |
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Application publication date: 20151125 |