CN106555249A

CN106555249A - Polyamide monofilament and its preparation method and application

Info

Publication number: CN106555249A
Application number: CN201510642948.1A
Authority: CN
Inventors: 郑毅; 秦兵兵; 冯淑芹; 刘修才
Original assignee: Shanghai Cathay Biotechnology Research and Development Center Co Ltd; Cathay Industrial Biotech Ltd
Current assignee: Cathay Wusu Biomaterial Co ltd; Cathay R&D Center Co Ltd; CIBT America Inc
Priority date: 2015-09-30
Filing date: 2015-09-30
Publication date: 2017-04-05
Anticipated expiration: 2035-09-30
Also published as: CN106555249B

Abstract

The invention provides a kind of polyamide monofilament and its preparation method and application, the raw materials for production of the polyamide monofilament at least contain polyamide, and the polyamide is at least made up of raw materials for production of 1,5- pentanediamines and aliphatic long carbochain biatomic acid；The production method of the polyamide monofilament comprises the steps：By dried polyamide through spinneret operation, cooling shaping, drafting process and winding sizing, polyamide monofilament is obtained；The raw materials for production of the polyamide monofilament of the present invention contain odd numbers of carbon atoms monomer, therefore the intermolecular formation hydrogen bond ratio of amide groups and crystal formation and strand space arrangement are different from the traditional polyamide monofilament with even-numbered carbon atom monomer as raw materials for production, compared with traditional polyamide monofilament, the polyamide monofilament of the present invention has the bending springback rate of lower initial modulus and Geng Gao, can be used for preparing super soft silk, and extend its service life.

Description

Polyamide monofilament and its preparation method and application

Technical field

The invention belongs to polyamide material technical field, is related to a kind of polyamide monofilament and its preparation method and application.

Background technology

The monfil by made by polyamide material is because wearability is good and resilience is good, therefore can be used to prepare the brush filament of hairbrush. For example, it is common by nylon 6, NYLON610 or brush filament made by nylon 612 on the market.

For the brush filament by made by nylon 6, although which has preferable wearability and resilience, but its water imbibition is high, Permanent deformation is easily produced under wet environment, therefore durability is not good.

For the brush filament by made by NYLON610 and nylon 612, although its water absorption rate is relative to the brush filament by made by nylon 6 Speech decreases, but the two is substantially all using the derivative of oil as raw materials for production, for example, caprolactam and adipic acid or Hexamethylene diamine.The series reaction such as reoxidize through hydrogenation as caprolactam and adipic acid are benzene class homologues to be obtained, hexamethylene diamine is Butadiene or acrylonitrile elder generation Adiponitrile are prepared by catalytic hydrogenation method again, therefore, the production technology of the brush filament on the whole compared with Complexity, does not only exist certain pollution, and also relies on the non-renewable resources such as oil.

The content of the invention

First purpose of the present invention is to provide a kind of while with good wearability, higher resilience, relatively low water suction The non-petroleum base polyamide monofilament of property and longer service life.

Second object of the present invention is to provide a kind of preparation method of above-mentioned polyamide monofilament, and the raw materials for production of the method are adopted The material in non-petroleum base source, will not produce with larger pollution, be conducive to environmental protection.

Third object of the present invention is to provide a kind of application of above-mentioned polyamide monofilament.

Fourth object of the present invention is to provide a kind of washing and brushing apparatus for having used above-mentioned polyamide monofilament.

To reach above-mentioned purpose, the solution of the present invention is：

A kind of polyamide monofilament, its raw materials for production at least contain polyamide, and the raw materials for production of polyamide at least contain 1,5- Pentanediamine.

Wherein, in a preferred embodiment of the invention, the raw materials for production of polyamide monofilament also containing other composition polymer and/or are helped Agent.

In a preferred embodiment of the invention, the raw materials for production of polyamide also contain aliphatic long carbochain biatomic acid.The fat The number of the carbon atom of race's long carbochain biatomic acid is preferably 10～18.For example, aliphatic long carbochain biatomic acid can for decanedioic acid, DC11, SL-AH, tridecanyldicarboxylic acid, DC14,15 carbon dicarboxylic acids, 16 carbon binary Any one or a few combination in acid, DC17, DC18 and △ 9-1,18- octadecylene binary acid.

In a preferred embodiment of the invention, 1,5- pentanediamines and aliphatic long carbochain biatomic acid can be made with biological fermentation process, The organic carbon of the renewable source for meeting ASTM D6866 standards can be contained.

In a preferred embodiment of the invention, polyamide is except containing by 1,5- pentanediamines and aliphatic long carbochain biatomic acid system Into polyamide outside, additive can also be contained.Additive includes but is not limited to antioxidant, heat-resisting stabilizing agent, weather resisting agent, face Material, gloss enhancer, dyestuff, crystal nucleating agent, delustering agent, plasticizer, antistatic additive, fire retardant, metal and slaine Deng.Above-mentioned additive can select an addition, it is also possible to add in any combination.

When polyamide contains polyamide and additive, the addition of polyamide should be not less than polyamide gross weight 50% and additive addition should be less than polyamide gross weight 50%；However, it is also possible to preferred polyamide adds Dosage is not less than the addition of the 70% of polyamide gross weight and additive less than the 30% of polyamide gross weight.

In a preferred embodiment of the invention, polyamide can be preferably polyamide 510, polyamide 511, polyamide 512, poly- Any one or a few in acid amides 513, polyamide 514, polyamide 516 and polyamide 518.

In a preferred embodiment of the invention, the viscosity number of polyamide can be 100～400mL/g, can further for 120～ 240mL/g, can also be further 130～200mL/g, can also be 135～180mL/g.

In a preferred embodiment of the invention, the terminal amino group content of polyamide can be 5～100mol/ton, can also be 10～70mol/ton, can also be further 20～60mol/ton.

In a preferred embodiment of the invention, the initial modulus of polyamide monofilament can be 1400～4200MPa, can be further For 2000～3800MPa, can also be further 2600～3500MPa.

In a preferred embodiment of the invention, the bending springback rate of polyamide monofilament can with >=50%, can it is further >=60%, also Can it is further >=65%.

In a preferred embodiment of the invention, the diameter of polyamide monofilament can be 0.1～3.0mm.

In a preferred embodiment of the invention, the fracture strength of polyamide monofilament can be with >=4.5N, can further >=8N.

In a preferred embodiment of the invention, the elongation at break of polyamide monofilament can be 10～63%, can also be further 18～55%.

A kind of preparation method of polyamide monofilament, which comprises the steps：By dried polyamide through spinneret operation, Cooling shaping, drafting process and winding sizing, obtain polyamide monofilament.Wherein, polyamide is above mentioned polyamide Resin.

In a preferred embodiment of the invention, the preparation method of the polyamide contained by polyamide comprises the steps：

The polyamide salt aqueous solution is heated up under conditions of pH value is for 7.5～8.9 in polymeric kettle, when the pressure in polymeric kettle reaches 0.2～2.0Mpa starts exhaust, when temperature reaches 220～290 DEG C is evacuated to 0～-0.1Mpa, maintain the vacuum 0～ 60min, obtains polyamide.

In a preferred embodiment of the invention, spinneret operation comprises the steps：By it is dried polyamide sliced, plus Heat, melting and filament spinning component is sent into after extruding, high pressure spinneret is forming filament.

In a preferred embodiment of the invention, drafting process includes at least twice drafting process, second drawing-off and first drawing-off Ratio be 2～7.

Polyamide monofilament can be applied in the brush filament for prepare washing and brushing apparatus.For example, the washing and brushing apparatus can be toothbrush or wiping Scrub；Now, the diameter of every brush filament can be preferably 0.15～0.35mm.

A kind of washing and brushing apparatus, the brush filament on its brush can be made up of above-mentioned polyamide monofilament.The washing and brushing apparatus can be toothbrush Or ecouvillon；Now, the diameter of every brush filament can be preferably 0.15～0.35mm.

Due to adopting such scheme, the invention has the beneficial effects as follows：

First, the raw materials for production of the polyamide monofilament of the present invention contain odd numbers of carbon atoms monomer, the introducing of the odd numbers of carbon atoms monomer Hydrogen bond ratio and space structure and crystal formation between polyamide molecule are changed effectively, which is in polymerization, spinning technique and filament properties On with it is traditional with even-numbered carbon atom monomer as raw materials for production made by polyamide monofilament (such as polyamide 66 or polyamide 612 etc.) It is very different.

Second, the raw materials for production of the polyamide monofilament of the present invention at least contain 1,5- pentanediamines and aliphatic long carbochain biatomic acid, and two Person can be made with biological fermentation process, can contain the organic carbon of the renewable source for meeting ASTM D6866 standards, therefore, The polyamide monofilament of the present invention is green material, does not rely on petroleum resources and serious pollution is not caused to environment.

3rd, with it is traditional with even-numbered carbon atom monomer as raw materials for production made by compared with polyamide monofilament, the polyamide of the present invention Monofilament has relatively low initial modulus (preferable pliability) and higher elastic recoil rate (preferable lodging resistance)；In addition, By the selection to polyamide viscosity number and draw ratio, its initial modulus and elastic recoil rate can be further adjusted, so as to open up Wide its use range.

Specific embodiment

The present invention relates to a kind of polyamide and preparation method thereof, the polyamide monofilament containing this kind of polyamide, the polyamides The preparation method and application of amine monofilament, and used the washing and brushing apparatus of the polyamide monofilament.

The raw materials for production of the polyamide of the present invention are at least containing the polyamide by made by the raw material such as diamine and binary acid.However, As the case may be, additive can also be contained in the raw materials for production of polyamide, but needs the addition of guarantee polyamide not The 50% of polyamide gross weight is less than less than the addition of 50% and additive of polyamide gross weight, can be with excellent The addition of 70% and additive that the addition for electing polyamide as is not less than polyamide gross weight is less than polyamide The 30% of gross weight.

[diamine]

In the present invention, diamine is preferably 1,5- pentanediamines.

Wherein, 1,5- pentanediamines can be prepared by chemical method, but are preferably by bioanalysis preparation.Bioanalysis includes adopting organism-based raw material Jing bioconversion methods (such as fermentation method, enzyme transforming process) are producing 1,5- pentanediamines；Or adopt petroleum-based feedstock Jing bioconversions Method produces 1,5- pentanediamines；Or 1,5- pentanediamines are produced using organism-based raw material Jing chemical methodes.Thus, pentanediamine contains and meets The organic carbon of the renewable source of ASTM D6866 standards.

Specifically, can slough by lysine or lysine salt in the presence of lysine decarboxylase (such as EC 4.1.1.18) After the carboxyl at two ends, you can produce 1,5- pentanediamines, such as " 1B decarboxylation enzymatic property and application study ", (Jiang Lili, Nanjing are big Learn, Master's thesis) in disclose the method that specific bioanalysis prepares pentanediamine；And for example " microorganism conversion 1B is cadaverine Research " (Zhu Jing, University Of Science and Technology Of Tianjin, Master's thesis, 2009.3) in also disclose that specific bioanalysis prepares pentanediamine Method.

[binary acid]

In the present invention, binary acid is preferably aliphatic long carbochain biatomic acid, and its carbon atom number can be preferably 10～18, example Such as, aliphatic long carbochain biatomic acid can be preferably decanedioic acid, DC11, SL-AH, tridecanyldicarboxylic acid, DC14,15 carbon dicarboxylic acids, 16-dicarboxylic acid, DC17, DC18 and △ 9-1,18- ten Any one or a few combination in eight alkene binary acid, can also be more preferably decanedioic acid or SL-AH.

In the present invention, aliphatic long carbochain biatomic acid can also be made up of chemical method, but is preferably made up of bioanalysis, for example, Bioanalysis can include using organism-based raw material Jing bioconversion methods (such as fermentation method, enzyme transforming process) producing the long carbon of aliphatic Chain binary acid；Or aliphatic long carbochain biatomic acid is produced using petroleum-based feedstock Jing bioconversion methods；Or adopt bio-based Raw material Jing chemical methodes production aliphatic long carbochain biatomic acid (such as decanedioic acid etc.).Thus, aliphatic long carbochain biatomic acid also may be used Organic carbon containing the renewable source for meeting ASTM D6866 standards.

[additive]

In the present invention, according to actually used needs, the raw materials for production of polyamide are except including above-mentioned diamine and two First acid is outer, can also include various additives.These additives include but is not limited to antioxidant, heat-resisting stabilizing agent, weather resisting agent, Pigment, gloss enhancer, dyestuff, crystal nucleating agent, delustering agent, plasticizer, antistatic additive, fire retardant, metal and metal Salt etc..Above-mentioned additive can select an addition, it is also possible to add in any combination.

Wherein, heat-resisting stabilizing agent is included but is not limited to based on the compound of hindered phenol, based on the compound of quinhydrones, based on thiazole Compound, the compound (such as phenyl-phosphonic acid) based on phosphorus, the compound (such as 2-mercaptobenzimidazole) and its replacement based on imidazoles Product, copper halide and iodine compound etc..

Weather resisting agent includes but is not limited to resorcinol, salicylate, BTA, benzophenone and hindered amine etc..

Pigment includes but is not limited to cadmium sulfide, phthalocyanine and carbon black etc..

Gloss enhancer includes but is not limited to titanium oxide and calcium carbonate etc..

Dyestuff includes but is not limited to Ni Gehei and nigrosine etc..

Crystal nucleating agent includes but is not limited to talcum, silica, kaolin and clay etc..

Plasticizer is included but is not limited to oxybenzoic acid monooctyl ester and N-butylbenzenesulfonamide etc..

Antistatic additive include but is not limited to alkyl sulphate type anionic antioxidant, quaternary ammonium salt cationic type antistatic additive, Non-ionic antistatic agent (such as polyoxyethylene sorbitan monostearate) and the both sexes antistatic additive based on glycine betaine etc..

Fire retardant include but is not limited to melamine cyanurate, hydroxide (such as magnesium hydroxide or aluminium hydroxide), ammonium polyphosphate, Brominated Polystyrene, brominated polyphenylether, brominated polycarbonate, brominated epoxy resin, by any fire retardant based on bromine and three oxygen Change combination of two antimony composition etc..

[polyamide]

In the polyamide of the production present invention, it is ensured that at least one in 1,5- pentanediamine and aliphatic long carbochain biatomic acid It is biobased products.

The polyamide of the present invention can be the polyamide of 5X containing polyamide (X >=10), more preferably can also contain Appointing in polyamide 510, polyamide 511, polyamide 512, polyamide 513, polyamide 514, polyamide 516 and polyamide 518 Anticipate the polyamide of one or more.Hereinafter only illustrate by taking polyamide 510 and polyamide 512 as an example.Remaining type it is poly- The situation of acid amides is equally treated with polyamide 510 or polyamide 512.

For example, polyamide 510 is at least made up of raw materials for production with 1,5- pentanediamines and decanedioic acid.When polyamide is also containing addition During agent, the addition P of polyamide 510₁50% (i.e. 50%≤P of polyamide gross weight should be not less than₁≤ 100%), now, The addition A of additive₁50% (i.e. 0%≤A of polyamide gross weight should be less than₁＜ is 50%)；Can also be to above-mentioned addition Amount carries out following preferred, the i.e. addition P of polyamide 510₁70% (i.e. 70%≤P of polyamide gross weight can be not less than₁ ≤ 100%), and now, the addition A of additive₁30% (i.e. 0%≤A of polyamide gross weight should be less than₁＜ is 30%).

Again for example, polyamide 512 is at least made up of raw materials for production with 1,5- pentanediamines and SL-AH.When polyamide also During containing additive, the addition P of polyamide 512₂50% (i.e. 50%≤P of polyamide gross weight should be not less than₂≤ 100%), Now, the addition A of additive₂50% (i.e. 0%≤A of polyamide gross weight should be less than₂＜ is 50%)；Can also be to upper Stating addition carries out following preferred, the i.e. addition P of polyamide 512₂The 70% (i.e. 70% of polyamide gross weight can be not less than ≤P₂≤ 100%), and now, the addition A of additive₂30% (i.e. 0%≤A of polyamide gross weight should be less than₂＜ is 30%).

Again for example, when polyamide 510, polyamide 512 and additive is contained in polyamide simultaneously, polyamide 510 and polyamides Addition sum P of amine 512₃50% (i.e. 50%≤P of polyamide gross weight should be not less than₃≤ 100%), and now, additive Addition A₃50% (i.e. 0%≤A of polyamide gross weight should be less than₃＜ is 50%)；Above-mentioned addition can also be carried out It is following preferably, i.e. addition sum P of polyamide 512 and polyamide 512₃The 70% of polyamide gross weight can be not less than (i.e. 70%≤P₃≤ 100%), and now, the addition A of additive₃30% (i.e. 0%≤A of polyamide gross weight should be less than₃＜ 30%).

[production method of polyamide]

Polyamide (i.e. at least with 1,5- pentanediamines and aliphatic long carbochain biatomic acid as raw materials for production) in the present invention can be with Made by fusion method or solution thermal polycondensation process.Various technological parameters can adjust according to performance need in preparation process, for example：It is poly- The concentration and pH value of acid amides saline solution, polymerization temperature, polymerization pressure, polymerization vacuum etc..

In a preferred embodiment of the invention, the production method of polyamide contained in polyamide comprises the steps：

(1) 100 liters of polymeric kettles (K/SY166-2007 types) are used into nitrogen displacement air, quality needed for adding in reactor Pure water, be subsequently adding a certain amount of 1,5- pentanediamines (can include meet ASTM D6866 standards renewable source it is organic Carbon), the aliphatic long carbochain biatomic acid (carbon number can be 10～18) of equimolar amounts after stirring, is added, with a small amount of 1,5- Pentanediamine and aliphatic long carbochain biatomic acid adjust pH value to 7.5～8.9 and (take nylon saline solution and be diluted to 10% detection pH Value), nylon saline solution (the polyamide salt aqueous solution i.e. mentioned above) is obtained.

(2), in a nitrogen environment, using oil bath heating, in kettle to be polymerized, pressure rises to 0.2～2.0Mpa, starts exhaust, treats When temperature in the kettle reaches 220～290 DEG C, 0～-1Mpa is evacuated to, keeps 0～60min of the vacuum, corresponding species is obtained Polyamide.

(3), nitrogen is filled with to 0.4～0.5Mpa of pressure into polymeric kettle, start melting discharging, and granulated using pelleter, into For polyamide cut into slices, 110 DEG C be dried vacuum drying 24 hours after plastic sealing pack.

Wherein, in step (1), after pH value is adjusted, can also add as the case may be equivalent to fatty clan elder The sodium hypophosphite of carbochain binary acid and 1,5- pentanediamine gross weights 100-200ppm.

[property of polyamide]

The property of the polyamide of the present invention is as follows：

(1), viscosity number

In the present invention, the viscosity number of polyamide is measured by Ubbelohde viscometer sulphate method, and its step is as follows：Accurately Dried polyamide sample (such as polyamide 66, polyamide 510 or polyamide 512 etc.) 0.25 ± 0.0002g is weighed, The 50mL concentrated sulfuric acids (96%) dissolving is added, the flow time t of the concentrated sulfuric acid is measured and recorded in 25 DEG C of constant temperature water baths₀With it is poly- The flow time t of amide resin sample solution.

Viscosity number computing formula is：Viscosity number VN=(t/t₀‐1)/C；

T-solution flow time；

t₀- solvent flow time；

The concentration (g/mL) of C-polymer.

Understand through test, the polyamide of the present invention can be with the viscosity number of 100～400mL/g in 96% sulfuric acid, also Can be with the viscosity number of 120～240mL/g in 96% sulfuric acid, it may be preferred to be with 96% sulfuric acid 130～200 The viscosity number of mL/g, viscosity number that can also be more preferably with 135～180mL/g in 96% sulfuric acid.

During polyamide monofilament is prepared, the viscosity number of polyamide should be controlled within the specific limits, if viscosity number is too low, Then the ropiness of polyamide is poor, may cause in spinneret operation cannot the situation of smooth drawing fiber silk occur；If viscous Number is too high, then the hypertonia of filament spinning component, and certain impact also can be produced on smooth wire drawing.Meanwhile, viscosity number is to polyamide monofilament Mechanical strength, the parameter such as bending springback rate or initial modulus will also result in certain impact, therefore, polyamide is glued Number needs to carry out above-mentioned preferred.

(2), terminal amino group content

In the present invention, the terminal amino group content of polyamide is determined by the following method, and the method comprises the steps：By 1g Polyamide is cut into slices, And with the 0.02mol/L hydrochloric acid acid-base titration solution, it is determined that amount H of 0.02mol/L hydrochloric acid used₁.Blank uses 0.02mol/L hydrochloric acid Above-mentioned phenol/alcohol mixed solvent is titrated, and determines amount H of 0.02mol/L hydrochloric acid₂.By H₁And H₂Between difference, calculate every Terminal amino group content in 1 ton of polyamide sample.

Understand through test, the terminal amino group content of the polyamide of the present invention can be 5～100mol/ton, can also for 10～ 70mol/ton, can also be preferably 20～60mol/ton.

In the course of the polymerization process, due to the restriction of the equilibrium constant, terminal amino group content is difficult to be reduced to below 10mol/ton, while necessarily Terminal amino group content be conducive to improving the resistance to ag(e)ing of polyamide and make polyamide and additive that there is preferable active force, from And contribute to the lifting of polyamide overall performance, therefore, the terminal amino group content of polyamide is carried out above-mentioned preferred.

The raw materials for production of the polyamide monofilament of the present invention at least contain above-mentioned polyamide.However, as the case may be, gather Can also be containing other composition polymer and/or auxiliary agent in the raw materials for production of acid amides monofilament.

[other composition polymer]

In the present invention, other composition polymer are except by the polyamides that 1,5- pentanediamines are outer and aliphatic long carbochain biatomic acid is prepared into Other compounds outside amine.

(1), other composition polymer can be containing the construction unit derived from following component：Aliphatic carboxylic acid (as oxalic acid, third Diacid, butanedioic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid etc.), alicyclic dicarboxylic acid (such as cyclohexyl dicarboxylic acid etc.) or Aromatic dicarboxylic acid is (such as terephthalic acid (TPA), M-phthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, anthracene dicarboxylic acids, luxuriant and rich with fragrance dicarboxyl Acid, diphenyl ether dicarboxylic acids, diphenoxyethanedicarboxylic acid, diphenylethane dicarboxylic acids, 1,4 cyclohexane dicarboxylic acid, 5- sodium sulfo groups M-phthalic acid, 5- 4-butyl-phosphonium M-phthalic acids etc.) etc..

(2), other composition polymer can be containing the construction unit derived from following component：Aliphatic diamine (as ethylenediamine, 1,3- diaminopropanes, 1,4- diaminobutanes, 1,6- diamino hexanes, 1,7- diaminoheptanes, 1,8- diamino-octanes, 1,9- Diamino nonane, 1,10- diamino decanes, 1,11- diamino undecanes, 1,12- diamino dodecanes, 1,13- diaminourea tridecanes, The 1,14- diaminourea tetradecanes, 1,15- diaminourea pentadecanes, 1,16- diaminourea hexadecanes, 1,17- diaminourea heptadecanes, 1,18- diaminos Base octadecane, 1,19- diaminourea nonadecanes, 1,20- diaminourea eicosane or 2- methyl isophthalic acids, 5- pentanediamines etc.), alicyclic diamine (such as Cyclohexanediamine or double-(4- Aminohexyls) methane etc.) or aromatic diamine (such as benzene dimethylamine etc.) etc..

(3), other composition polymer can be containing the construction unit derived from following component：Aromatic series, aliphatic or alicyclic Diol compound is (such as ethylene glycol, propane diols, butanediol, pentanediol, hexylene glycol, 1,4- cyclohexanedimethanols, neopentyl glycol, hydrogen Double (4- hydroxy phenyls) propane of quinone, resorcinol, dihydroxybiphenyl, naphthalene glycol, anthracene glycol, luxuriant and rich with fragrance glycol, 2,2-, 4,4 '-two Hydroxy diphenyl ether or bisphenol S etc.) etc..

(4), other composition polymer can be containing the construction unit derived from following component：Aromatic series with hydroxyl and carboxylic acid Compound, aliphatic compound or cycloaliphatic hydroxyl group carboxylic acid compound etc..Wherein, cycloaliphatic hydroxyl group carboxylic acid includes but is not limited to breast Acid, 3- hydroxy propionates, 3-hydroxybutyrate ester, 3-hydroxybutyrate ester-valerate, hydroxybenzoic acid, hydroxyl naphthalene-carboxylic acid, hydroxyl Anthracene carboxylic acid, hydroxyl phenanthrene carboxylic acid and (hydroxy phenyl) vinyl carboxylic acid etc..

(5), other composition polymer can be containing the construction unit derived from following component：Amino acid (as 6-aminocaprolc acid, 11- amino undecanoic acids, 12 amino dodecanoic acid or PAMBA etc.) or lactams (as epsilon-caprolactams or ε- Lauric lactam etc.) etc..

(6), other composition polymer can for can with 1,5- pentanediamines and the comonomer of aliphatic long carbochain biatomic acid copolymerization, The comonomer include but is not limited to amino acid, lactams, aromatic dicarboxylic acid, aliphatic dicarboxylic acid, alicyclic dicarboxylic acid, Aromatic diol, aliphatic diol, alicyclic diol, aromatic diamine, aliphatic diamine, alicyclic diamine, aromatic series hydroxyl Yl carboxylic acid, aliphatic hydroxyl carboxylic acid, cycloaliphatic hydroxyl group carboxylic acid and the respective derivative of above-mentioned comonomer.Wherein, it is above-mentioned common The respective derivative of polycondensation monomer includes the product of above-mentioned any two kinds of comonomers reaction, for example, one of a molecule diamines Product of one carboxyl reaction of amino and a molecule dicarboxylic acids into salt.

[property of polyamide monofilament]

The property of the polyamide monofilament of the present invention is as described below：

(1), filament diameter

The assay method of the polyamide monofilament in the present invention is：Average after detecting at 10 points with slide measure.

The diameter of the polyamide monofilament in the present invention can be 0.1～3.0mm.The diameter of polyamide monofilament is had with its application Close, bigger its intensity of diameter is also bigger.When polyamide monofilament is used as tooth brush monofilament, its diameter can be 0.15～0.35mm；When When polyamide monofilament is used as netting twine, its diameter can be 0.1～1.0mm；When polyamide monofilament is used as silkworm gut, its diameter Can be 0.15～3.0mm.

(2), fracture strength

The fracture strength of the polyamide monofilament in the present invention presses GB/T21032-2007 methods measure.

The fracture strength of the polyamide monofilament in the present invention is >=4.5N, preferably >=8N.Using the difference in field, it is right to determine The difference of the requirement of the fracture strength of polyamide monofilament.Can pass through to adjust the technological parameters such as the viscosity number and draw ratio of polyamide To adjust jointly the fracture strength of polyamide monofilament.Viscosity number and/or draw ratio are bigger, and fracture strength is bigger.

(3), elongation at break

The elongation at break of the polyamide monofilament in the present invention presses GB/T21032-2007 methods measure.

The elongation at break of the polyamide monofilament in the present invention can be 10～63%, can also be preferably 18～55%.

(4), initial modulus

Initial modulus is the common counter in monofilament detection, which represent the pliability of silk.At the beginning of polyamide monofilament in the present invention Beginning modulus is pressed GB/T21032-2007 methods and determines stress strain curve, and it is initial modulus to take modulus of the polyamide monofilament when extending 1%.

The initial modulus of the polyamide monofilament of the present invention is preferably 1400～4200MPa, can also be more preferably 2000～ 3800MPa, can also be more preferably 2600～3500MPa.

In research process, inventor is surprised to find that：If with odd numbers of carbon atoms monomer (such as 1,5- pentanediamines) as raw materials for production system Standby Long Carbon Chain Polyamide monofilament, then the initial modulus of the Long Carbon Chain Polyamide monofilament significantly lower than with traditional even-numbered carbon atom monomer be Polyamide monofilament obtained in raw materials for production, this is likely due to the introducing of odd numbers of carbon atoms monomer so that amido link cannot be completely formed Intermolecular hydrogen bonding, causes soft segment elongated.This is found to be and prepares super soft polyamide monofilament there is provided possibility.If while coordinating The parameters such as the draw ratio of viscosity number and drafting process of polyamide are adjusted, the introductory die of the polyamide monofilament can be further reduced Amount properly increases its initial modulus, such that it is able to prepare the polyamide with different initial modulus according to specific needs respectively Monofilament, provides possibility for its application in different field.In the range of application of brush filament, viscosity number and/or draw ratio are lower, just Beginning modulus is lower.

(5), bending springback rate

Bending springback rate is very important index in fields such as brush filaments, embodies the lodging resistance of brush filament.In general, curved Bent rebound degree is higher, and service life is longer, and quality is better.

The bending springback rate of the polyamide monofilament in the present invention is measured by the following method, and the method comprises the steps：At one piece On metallic plate, the through hole of three a diameter of 1.5mm is made a call to, by the soft blunt of three polyamide monofilaments from polyamide monofilament Between advanced it in three holes respectively, elbow part is concordant with the opposite side of metallic plate, then puts the 2min into 50 DEG C of water, then puts Enter in 20 DEG C of water after 0.5min, polyamide monofilament is taken out from through hole, recovers 15min in being put into 20 DEG C of water, after taking-up Measurement table angle, is bent rebound degree.In the same manner, be made up of polyamide monofilament any multifilament (as tooth brush monofilament, shoe brush silk or Cleaning brush filament etc.) bending springback rate can determine in aforementioned manners.

The bending springback rate of the polyamide monofilament in the present invention can be preferably >=50%, can also be more preferably >=60%, also Can still more preferably be >=65%.

In spinning process, inventor is surprised to find that：Under similar conditions, using the poly- of 5X containing polyamide (X >=10) The bending springback rate of the polyamide monofilament obtained by amide resin is higher than the polyamide using X containing polyamide 6 (X >=10) Obtained polyamide monofilament, this is that the theoretical institute of traditional chain length is unaccountable.Inventor thinks：This phenomenon Producing reason After possibly odd numbers of carbon atoms monomer (such as 1,5- pentanediamines) is introduced as raw materials for production, amido link half forms intermolecular hydrogen bonding, The soft point of so amido link can obtain the support of alkane segment, and then increase its bending springback rate.

[preparation method of polyamide monofilament]

The preparation method of the polyamide monofilament of the present invention comprises the steps：

(1), above-mentioned polyamide is dried, and filament is obtained through spinneret operation；

(2) above-mentioned filament is sequentially passed through into cooling shaping, drafting process and winding sizing, polyamide monofilament is obtained.

Wherein, in step (1), spinneret operation includes：Dried polyamide is cut into slices, gained section is connected In continuous feeding single-screw extrusion machine, then heating, melting and filament spinning component is sent into after extruding, high pressure spinneret is forming above-mentioned fibre Dimension silk.

In above-mentioned spinneret operation, the temperature of single screw extrusion machine zonal control vertically, area's heating-up temperature is 220～ 270 DEG C, two area's heating-up temperatures be 225～310 DEG C, three-zone heating temperature be 230～310 DEG C, four area's heating-up temperatures be 240～ 300 DEG C, five area's heating-up temperatures are 240～290 DEG C, and six area's heating-up temperatures are 230～290 DEG C.The selection of the temperature range in each region Be according to polyamide section melting, mixing, mobility situations such as come comprehensive regulation.If temperature is too low, may cause Plastifying fusion is uneven, so that spinnability is deteriorated, if temperature is too high, can produce the side reactions such as decomposition, same to affect poly- The performance of the spinnability and polyamide monofilament of amide resin.

, at 230～290 DEG C, the temperature is according to into silk situation and supply pump pressure for the temperature general control of the spinning manifold of filament spinning component Adjust, the pressure rise of filament spinning component, or even damage equipment if temperature is too low, can be caused, form head silk, if temperature mistake Height, then easily cause degraded, not into silk the problems such as.

On the spinneret of filament spinning component, the cross sectional shape of the polyamide monofilament that the shape in the hole of spinning head is manufactured as needed is selected.This Invention preferably 44 hole spinnerets, discharge the polyamide monofilament with circular section shape with uniform.However, it is also possible to according to reality Situation is adjusted.

In step (2), during cooling shaping, the solidification method cooling that the solidification method or cooling air of cold water is usually used is spun Into filament, the preferably solidification method of cold water.In the present invention, make to be spun into filament and fall into cooling shaping in 33 DEG C of water-baths.

In step (2), drafting process includes：The filament after cooling shaping is taken, and nearly boiling water bath is entered (about Jing after one drawing-off 85 DEG C) after carry out two road drawing-offs, the control of twice draw ratio is 2～7.Twice draw ratio is second drawing-off and first drawing-off Ratio.

Through substantial amounts of experiment, inventor is it was unexpectedly observed that draw ratio has very big shadow for the initial modulus of polyamide monofilament Ring, when draw ratio is relatively low, initial modulus is relatively low, after draw ratio is improved, initial modulus also occurs different degrees of raising, the parameter Contribute to adjust polyamide monofilament initial modulus, so as to obtain can use under various circumstances with different initial modulus Polyamide monofilament.

In step (2), winding sizing includes：The silk formed through drafting process is wound in square circle, is shifted after full volume Carry out thermal finalization 0.5 hour into 110 DEG C of steam coppers, be finally transferred in 50 DEG C of drying rooms and be dried, obtain polyamide monofilament (into Product).The heat setting temperature and time can be adjusted as the case may be.

Below in conjunction with preparation example, embodiment and comparative example, the present invention is further illustrated.

Preparation example one (polyamide 510)

This preparation example provides a kind of preparation method of polyamide 510, and which comprises the steps：

(1) 100 liters of polymeric kettles (K/SY166-2007 types) are used into nitrogen displacement air, 30kg pure water are added in reactor, 10.06kg (98.5mol) 1,5- pentanediamines (organic carbon comprising the renewable source for meeting ASTM D6866 standards) are subsequently adding, After stirring, 19.93kg (98.5mol) decanedioic acid is added, pH value is adjusted to 8.43 with a small amount of 1,5- pentanediamines and decanedioic acid (take nylon saline solution and be diluted to 10% detection pH value), is obtained nylon saline solution；

(2), in a nitrogen environment, using oil bath heating, oil bath temperature is progressively risen to 280 DEG C, pressure liter in kettle to be polymerized To 1.73Mpa, start exhaust, when temperature in the kettle reaches 265 DEG C, be evacuated to -0.06Mpa, keep vacuum 20min, Prepared polyamide 510；

(3), nitrogen is filled with to pressure 0.4Mpa into polymeric kettle, start melting discharging, and granulated using pelleter, 110 DEG C It is dried plastic sealing pack after being vacuum dried 24 hours.

Preparation example two (polyamide 510)

(1) 100 liters of polymeric kettles (K/SY166-2007 types) are used into nitrogen displacement air, in reactor, adds 12.8kg pure Water, is subsequently adding 10.06kg (98.5mol) 1,5- pentanediamines (comprising having for the renewable source for meeting ASTM D6866 standards Machine carbon), after stirring, 19.93kg (98.5mol) decanedioic acid is added, pH value is adjusted with a small amount of 1,5- pentanediamines and decanedioic acid To 8.20 (take nylon saline solution and be diluted to 10% detection pH value), nylon saline solution is obtained；

(2), in a nitrogen environment, using oil bath heating, oil bath temperature is progressively risen to 280 DEG C, pressure liter in kettle to be polymerized To 1.0Mpa, start exhaust, when temperature in the kettle reaches 265 DEG C, be evacuated to -0.055Mpa, keep vacuum 20min, Prepared polyamide 510；

Preparation example three (polyamide 510)

(1) 100 liters of polymeric kettles (K/SY166-2007 types) are used into nitrogen displacement air, in reactor, adds 12.8kg pure Water, is subsequently adding 10.06kg (98.5mol) 1,5- pentanediamines (comprising having for the renewable source for meeting ASTM D6866 standards Machine carbon), after stirring, 19.93kg (98.5mol) decanedioic acid is added, pH value is adjusted with a small amount of 1,5- pentanediamines and decanedioic acid To 8.22 (take nylon saline solution and be diluted to 10% detection pH value), nylon saline solution is obtained；

(2), in a nitrogen environment, using oil bath heating, oil bath temperature is progressively risen to 280 DEG C, pressure liter in kettle to be polymerized To 1.0Mpa, start exhaust, when temperature in the kettle reaches 265 DEG C, be evacuated to -0.065Mpa, keep vacuum 20min, Prepared polyamide 510；

Preparation example four (polyamide 510)

(1) 100 liters of polymeric kettles (K/SY166-2007 types) are used into nitrogen displacement air, in reactor, adds 12.8kg pure Water, is subsequently adding 10.06kg (98.5mol) 1,5- pentanediamines (comprising having for the renewable source for meeting ASTM D6866 standards Machine carbon), after stirring, 19.93kg (98.5mol) decanedioic acid is added, pH value is adjusted with a small amount of 1,5- pentanediamines and decanedioic acid To 8.5 (take nylon saline solution and be diluted to 10% detection pH value), add equivalent to binary acid (decanedioic acid) and diamine (1,5- Pentanediamine) gross weight 200ppm sodium hypophosphite, nylon saline solution is obtained；

(2), in a nitrogen environment, using oil bath heating, oil bath temperature is progressively risen to 288 DEG C, pressure liter in kettle to be polymerized To 1.2Mpa, start exhaust, when temperature in the kettle reaches 268 DEG C, be evacuated to -0.07Mpa, keep vacuum 25min, Prepared polyamide 510；

(3), nitrogen is filled with to pressure 0.5Mpa into polymeric kettle, start melting discharging, and granulated using pelleter, 110 DEG C It is dried plastic sealing pack after being vacuum dried 24 hours.

Preparation example five (polyamide 511)

This preparation example provides a kind of preparation method of polyamide 511, and which comprises the steps：

(1) 100 liters of polymeric kettles (K/SY166-2007 types) are used into nitrogen displacement air, in reactor, adds 12.8kg pure Water, is subsequently adding 9.63kg (94.2mol) 1,5- pentanediamines (comprising the organic of the renewable source for meeting ASTM D6866 standards Carbon), after stirring, 20.37kg (94.2mol) DC11 is added, will with a small amount of 1,5- pentanediamines and DC11 PH value is adjusted to 8.31 (take nylon saline solution and be diluted to 10% detection pH value), is added equivalent to binary acid (11 carbon two First acid) and diamine (1,5- pentanediamine) gross weight 100ppm sodium hypophosphite, prepared nylon saline solution；

(2), in a nitrogen environment, using oil bath heating, oil bath temperature is progressively risen to 280 DEG C, pressure liter in kettle to be polymerized To 1.73Mpa, start exhaust, when temperature in the kettle reaches 265 DEG C, be evacuated to -0.05Mpa, keep vacuum 20min, Prepared polyamide 511；

Preparation example six (polyamide 512)

In the present embodiment, except the binary acid adjusted in preparation example five is SL-AH, and adjusts its addition and be 20.78kg (90.2mol), the addition for adjusting 1,5- pentanediamines are 9.22kg (90.2mol), adjust PH and are 8.46 and are not added with Outside sodium hypophosphite, remaining step is identical with preparation example five, comprises the following steps that：

This preparation example provides a kind of preparation method of polyamide 512, and which comprises the steps：

(1) 100 liters of polymeric kettles (K/SY166-2007 types) are used into nitrogen displacement air, 12.8kg pure water are added in reactor, 9.22kg (90.2mol) 1,5- pentanediamines (organic carbon comprising the renewable source for meeting ASTM D6866 standards) are subsequently adding, After stirring, 20.78kg (90.2mol) SL-AH is added, pH value is adjusted with a small amount of 1,5- pentanediamines and SL-AH Save to 8.46 (take nylon saline solution and be diluted to 10% detection pH value), be added without sodium hypophosphite, nylon saline solution is obtained；

(2), in a nitrogen environment, using oil bath heating, oil bath temperature is progressively risen to 280 DEG C, pressure liter in kettle to be polymerized To 1.73Mpa, start exhaust, when temperature in the kettle reaches 265 DEG C, be evacuated to -0.05Mpa, keep vacuum 20min, Prepared polyamide 512.

Preparation example seven (polyamide 513)

In the present embodiment, except the binary acid adjusted in preparation example five is tridecanyldicarboxylic acid, and adjusts its addition and be 21.15kg (86.6mol), the addition for adjusting 1,5- pentanediamines are 8.85kg (86.6mol), adjust PH and are 8.44 and take out true Empty is that remaining step is identical with preparation example five, comprises the following steps that outside -0.06MPa：

(1) 100 liters of polymeric kettles (K/SY166-2007 types) are used into nitrogen displacement air, in reactor, adds 12.8kg pure Water, is subsequently adding 8.85kg (86.6mol) 1,5- pentanediamines (comprising the organic of the renewable source for meeting ASTM D6866 standards Carbon), after stirring, 21.15kg (86.6mol) tridecanyldicarboxylic acid is added, will with a small amount of 1,5- pentanediamines and tridecanyldicarboxylic acid PH value is adjusted to 8.44 (take nylon saline solution and be diluted to 10% detection pH value), is added equivalent to binary acid (13 carbon two First acid) and diamine (1,5- pentanediamine) gross weight 100ppm sodium hypophosphite, prepared nylon saline solution；

(2), in a nitrogen environment, using oil bath heating, oil bath temperature is progressively risen to 280 DEG C, pressure liter in kettle to be polymerized To 1.73Mpa, start exhaust, when temperature in the kettle reaches 265 DEG C, be evacuated to -0.06Mpa, keep vacuum 20min, Prepared polyamide 513；

Preparation example eight (polyamide 514)

In the present embodiment, except the binary acid adjusted in preparation example five is DC14, and adjusts its addition and be 21.50kg (83.2mol), adjust 1,5- pentanediamines addition be 8.50kg (83.2mol), adjustment PH be 8.58 outside, remaining Step is identical with preparation example seven, comprises the following steps that：

(1) 100 liters of polymeric kettles (K/SY166-2007 types) are used into nitrogen displacement air, in reactor, adds 12.8kg pure Water, is subsequently adding 8.05kg (83.2mol) 1,5- pentanediamines (comprising the organic of the renewable source for meeting ASTM D6866 standards Carbon), after stirring, 21.15kg (83.2mol) DC14 is added, will with a small amount of 1,5- pentanediamines and DC14 PH value is adjusted to 8.58 (take nylon saline solution and be diluted to 10% detection pH value), is added equivalent to binary acid (14 carbon two First acid) and diamine (1,5- pentanediamine) gross weight 100ppm sodium hypophosphite, prepared nylon saline solution；

(2), in a nitrogen environment, using oil bath heating, oil bath temperature is progressively risen to 280 DEG C, pressure liter in kettle to be polymerized To 1.73Mpa, start exhaust, when temperature in the kettle reaches 265 DEG C, be evacuated to -0.06Mpa, keep vacuum 20min, Prepared polyamide 514；

Preparation example nine (polyamide 516)

In the present embodiment, except the binary acid adjusted in preparation example seven is 16-dicarboxylic acid, and adjusts its addition and be 22.11kg (77.2mol), adjust 1,5- pentanediamines addition be 7.89kg (77.2mol), adjustment PH be 8.62 outside, remaining Step is identical with preparation example seven, comprises the following steps that：

(1) 100 liters of polymeric kettles (K/SY166-2007 types) are used into nitrogen displacement air, in reactor, adds 12.8kg pure Water, is subsequently adding 7.89kg (83.2mol) 1,5- pentanediamines (comprising the organic of the renewable source for meeting ASTM D6866 standards Carbon), after stirring, 22.11kg (77.2mol) 16-dicarboxylic acid is added, will with a small amount of 1,5- pentanediamines and 16-dicarboxylic acid PH value is adjusted to 8.62 (take nylon saline solution and be diluted to 10% detection pH value), is added equivalent to binary acid (16 carbon two First acid) and diamine (1,5- pentanediamine) gross weight 100ppm sodium hypophosphite, prepared nylon saline solution；

(2), in a nitrogen environment, using oil bath heating, oil bath temperature is progressively risen to 280 DEG C, pressure liter in kettle to be polymerized To 1.73Mpa, start exhaust, when temperature in the kettle reaches 265 DEG C, be evacuated to -0.06Mpa, keep vacuum 20min, Prepared polyamide 516；

Preparation example ten (polyamide 518)

In the present embodiment, except the binary acid adjusted in preparation example seven is DC18, and adjusts its addition and be 22.64kg (72.0mol), adjust 1,5- pentanediamines addition be 7.36kg (72.0mol), adjustment PH be 8.59 outside, remaining Step is identical with preparation example seven, comprises the following steps that：

(1) 100 liters of polymeric kettles (K/SY166-2007 types) are used into nitrogen displacement air, in reactor, adds 12.8kg pure Water, is subsequently adding 7.36kg (72.0mol) 1,5- pentanediamines (comprising the organic of the renewable source for meeting ASTM D6866 standards Carbon), after stirring, 22.64kg (72.0mol) DC18 is added, will with a small amount of 1,5- pentanediamines and DC18 PH value is adjusted to 8.59 (take nylon saline solution and be diluted to 10% detection pH value), is added equivalent to binary acid (18 carbon two First acid) and diamine (1,5- pentanediamine) gross weight 100ppm sodium hypophosphite, prepared nylon saline solution.

(2), in a nitrogen environment, using oil bath heating, oil bath temperature is progressively risen to 280 DEG C, pressure liter in kettle to be polymerized To 1.73Mpa, start exhaust, when temperature in the kettle reaches 265 DEG C, be evacuated to -0.06Mpa, keep vacuum 20min, Prepared polyamide 518.

Compare preparation example one (polyamide 66)

This compares preparation example there is provided a kind of preparation method of polyamide 66, and which comprises the steps：

(1) 100 liters of polymeric kettles (K/SY166-2007 types) are used into nitrogen displacement air, 30kg pure water are added in reactor, 13.28kg (114.3mol) hexamethylene diamine (organic carbon comprising the renewable source for meeting ASTM D6866 standards) is subsequently adding, After stirring, the own binary acid of 16.72kg (114.3mol) is added, pH value is adjusted to 7.83 with a small amount of hexamethylene diamine and adipic acid and (is taken Nylon saline solution is diluted to 10% detection pH value), nylon saline solution is obtained；

(2), in a nitrogen environment, using oil bath heating, oil bath temperature is progressively risen to 298 DEG C, pressure liter in kettle to be polymerized To 1.73Mpa, start exhaust, when temperature in the kettle reaches 275 DEG C, be evacuated to -0.04Mpa, keep vacuum 20min, Prepared polyamide 66；

Compare preparation example two (polyamide 612)

This compares preparation example there is provided a kind of preparation method of polyamide 612, and which comprises the steps：

(1) 100 liters of polymeric kettles (K/SY166-2007 types) are used into nitrogen displacement air, 45kg pure water are added in reactor, 10.06kg (86.5mol) hexamethylene diamine (organic carbon comprising the renewable source for meeting ASTM D6866 standards) is subsequently adding, After stirring, 19.93kg (86.5.5mol) SL-AH is added, pH value is adjusted with a small amount of hexamethylene diamine and SL-AH Save to 7.99 (take nylon saline solution and be diluted to 10% detection pH value), nylon saline solution is obtained.

(2), in a nitrogen environment, using oil bath heating, oil bath temperature is progressively risen to 280 DEG C, pressure liter in kettle to be polymerized To 1.73Mpa, start exhaust, when temperature in the kettle reaches 265 DEG C, be evacuated to -0.05Mpa, keep vacuum 20min, Prepared polyamide 612.

Preparation example one to preparation example ten and compare preparation example one and compare preparation example two preparation method each parameter such as table 1 below with Shown in table 2 below.The viscosity number and terminal amino group content of the polyamide obtained by preparation example one to preparation example ten is as shown in table 3.

Table 1 is preparation example one to preparation example ten and compares preparation example one and the addition scale for comparing each component in preparation example two

Table 2 is preparation example one to preparation example ten and the process parameter table for comparing preparation example one with the preparation method for comparing preparation example two

Table 3 is preparation example one to preparation example ten and the viscosity number for comparing preparation example one with the polyamide compared obtained by preparation example two With the numerical tabular of terminal amino group content

Species	Prepare product	Viscosity number (mL/g)	Terminal amino group content (mol/ton)
				Preparation example one	Polyamide 510	137.1	46.5
Preparation example two	Polyamide 510	149.3	49.6
				Preparation example three	Polyamide 510	167.2	42.8
Preparation example four	Polyamide 510	190.1	33.6
				Preparation example five	Polyamide 511	142.3	35.7
Preparation example six	Polyamide 512	135.2	45.1
				Preparation example seven	Polyamide 513	136.4	41
Preparation example eight	Polyamide 514	141.6	38.5
				Preparation example nine	Polyamide 516	138.7	42.6
Preparation example ten	Polyamide 518	136.7	41.8
				Compare preparation example one	Polyamide 66	142.1	42.1
Compare preparation example two	Polyamide 612	140.6	44.3

Embodiment one (510 monofilament of polyamide)

A kind of preparation method of 510 monofilament of polyamide is present embodiments provided, which comprises the steps：

(1) the section 20kg of polyamide 510 in preparation example one, is taken, is continuously fed in single-screw extrusion machine after being dried, heated, Extruding, it is melt into 510 fused mass of polyamide, single screw extrusion machine zonal control vertically, area's heating-up temperature is 270 DEG C, Two area's heating-up temperatures are 300 DEG C, three-zone heating temperature is 300 DEG C, and four area's heating-up temperatures are 300 DEG C, and five area's heating-up temperatures are 285 DEG C, six area's heating-up temperatures are 270 DEG C, and spinning body temperature is 266 DEG C；

(2), the spinning pump accurate measurement by 510 fused mass Jing melt distribution pipes of polyamide in spinning manifold, Jing are isometric Pipe is evenly distributed to 510 fused mass of polyamide (melt) in filament spinning component, and the melt mixed in filament spinning component is from spinning Circular spinneret (hole count the is 44 holes) high pressure of component bottom sprays to form filament；

(3), filament falls into cooling shaping in 33 DEG C of water-baths, is carried out after entering nearly boiling water bath (about 85 DEG C) Jing after one drawing-off Two road drawing-offs, twice draw ratio are controlled 3.6, are then wound in square circle, carry out heat in being transferred to 110 DEG C of steam coppers after full volume Sizing 0.5 hour, is finally transferred to 50 DEG C, 510 monofilament of polyamide is dried to obtain in drying room.

Embodiment two (510 monofilament of polyamide)

(1) the section 20kg of polyamide 510 in preparation example two, is taken, is continuously fed in single-screw extrusion machine after being dried, heated, Extruding, it is melt into 510 fused mass of polyamide, single screw extrusion machine zonal control vertically, area's heating-up temperature is 264 DEG C, Two area's heating-up temperatures are 298 DEG C, three-zone heating temperature is 298 DEG C, and four area's heating-up temperatures are 298 DEG C, and five area's heating-up temperatures are 280 DEG C, six area's heating-up temperatures are 266 DEG C, and spinning body temperature is 260 DEG C；

(3), filament falls into cooling shaping in 38 DEG C of water-baths, carries out two road drawing-offs after entering nearly boiling water bath Jing after one drawing-off, Twice draw ratio is controlled 3.5, is then wound in square circle, carries out thermal finalization, finally after full volume in being transferred to 100 DEG C of steam coppers 510 monofilament of polyamide is dried to obtain in being transferred to drying room.

Embodiment three (510 monofilament of polyamide)

In the present embodiment, in addition to the twice draw ratio in adjustment embodiment two is 4.5, other are grasped in the same manner as embodiment two Make, comprise the following steps that：

(3), filament falls into cooling shaping in 38 DEG C of water-baths, carries out two road drawing-offs after entering nearly boiling water bath Jing after one drawing-off, Twice draw ratio is controlled 4.5, is then wound in square circle, carries out thermal finalization, finally after full volume in being transferred to 100 DEG C of steam coppers 510 monofilament of polyamide is dried to obtain in being transferred to drying room.

Example IV (510 monofilament of polyamide)

(1) the section 20kg of polyamide 510 in preparation example three, is taken, after being dried, is continuously fed in single-screw extrusion machine, Jing adds Heat, extrude, be melt into 510 fused mass of polyamide, single screw extrusion machine zonal control vertically, area's heating-up temperature is 272 DEG C, Two area's heating-up temperatures are 305 DEG C, three-zone heating temperature is 305 DEG C, and four area's heating-up temperatures are 305 DEG C, and five area's heating-up temperatures are 290 DEG C, six area's heating-up temperatures are 271 DEG C, and spinning body temperature is 268 DEG C；

(3), filament falls into cooling shaping in 33 DEG C of water-baths, is carried out after entering nearly boiling water bath (about 85 DEG C) Jing after one drawing-off Two road drawing-offs, twice draw ratio are controlled 3.8, are then wound in square circle, carry out heat in being transferred to 110 DEG C of steam coppers after full volume Sizing 0.5 hour, is finally transferred to 50 DEG C, 510 monofilament of polyamide is dried to obtain in drying room.

Embodiment five (510 monofilament of polyamide)

(1), the polyamide 510 in preparation example four is cut into slices 20kg, after being dried, is continuously fed in single-screw extrusion machine, Jing adds Heat, extrude, be melt into 510 fused mass of polyamide, single screw extrusion machine zonal control vertically, area's heating-up temperature is 275 DEG C, Two area's heating-up temperatures are 305 DEG C, three-zone heating temperature is 310 DEG C, and four area's heating-up temperatures are 308 DEG C, and five area's heating-up temperatures are 295 DEG C, six area's heating-up temperatures are 280 DEG C, and spinning body temperature is 275 DEG C；

(3), filament falls into cooling shaping in 33 DEG C of water-baths, is carried out after entering nearly boiling water bath (about 85 DEG C) Jing after one drawing-off Two road drawing-offs, twice draw ratio are controlled 4.9, are then wound in square circle, carry out heat in being transferred to 110 DEG C of steam coppers after full volume Sizing 0.5 hour, is finally transferred to 50 DEG C, 510 monofilament of polyamide is dried to obtain in drying room.

Embodiment six (511 monofilament of polyamide)

(1) the section 20kg of polyamide 511 in preparation example five, is taken, after being dried, is continuously fed in single-screw extrusion machine, Jing adds Heat, extrude, be melt into 511 fused mass of polyamide, single screw extrusion machine zonal control vertically, area's heating-up temperature is 268 DEG C, Two area's heating-up temperatures are 300 DEG C, three-zone heating temperature is 298 DEG C, and four area's heating-up temperatures are 298 DEG C, and five area's heating-up temperatures are 282 DEG C, six area's heating-up temperatures are 268 DEG C, and spinning body temperature is 265 DEG C；

(2), the spinning pump accurate measurement by 510 fused mass Jing melt distribution pipes of polyamide in spinning manifold, Jing are isometric Pipe is evenly distributed to 511 fused mass of polyamide (melt) in filament spinning component, and the melt mixed in filament spinning component is from spinning Circular spinneret (hole count the is 44 holes) high pressure of component bottom sprays to form filament；

(3), filament falls into cooling shaping in 33 DEG C of water-baths, is carried out after entering nearly boiling water bath (about 85 DEG C) Jing after one drawing-off Two road drawing-offs, twice draw ratio are controlled 3.8, are then wound in square circle, carry out heat in being transferred to 110 DEG C of steam coppers after full volume Sizing 0.5 hour, is finally transferred to 50 DEG C, 511 monofilament of polyamide is dried to obtain in drying room.

Embodiment seven (512 monofilament of polyamide)

In the present embodiment, it is the polyamide 512 in preparation example six except adjusting polyamide 511 in embodiment six, other and enforcement Example six is similarly operated, and is comprised the following steps that：

(1) the section 20kg of polyamide 512 in preparation example six, is taken, after being dried, is continuously fed in single-screw extrusion machine, Jing adds Heat, extrude, be melt into 511 fused mass of polyamide, single screw extrusion machine zonal control vertically, area's heating-up temperature is 268 DEG C, Two area's heating-up temperatures are 300 DEG C, three-zone heating temperature is 298 DEG C, and four area's heating-up temperatures are 298 DEG C, and five area's heating-up temperatures are 282 DEG C, six area's heating-up temperatures are 268 DEG C, and spinning body temperature is 265 DEG C；

(3), filament falls into cooling shaping in 33 DEG C of water-baths, is carried out after entering nearly boiling water bath (about 85 DEG C) Jing after one drawing-off Two road drawing-offs, twice draw ratio are controlled 3.8, are then wound in square circle, carry out heat in being transferred to the steam coppers of volume 110 after full volume Sizing 0.5 hour, is finally transferred to 50 DEG C, 511 monofilament of polyamide is dried to obtain in drying room.

Embodiment eight (513 monofilament of polyamide)

In the present embodiment, except the polyamide 511 adjusted in embodiment six is the polyamide 513 in preparation example seven, other and reality Apply example six similarly to operate, comprise the following steps that：

(1) the section 20kg of polyamide 513 in preparation example seven, is taken, after being dried, is continuously fed in single-screw extrusion machine, Jing adds Heat, extrude, be melt into 511 fused mass of polyamide, single screw extrusion machine zonal control vertically, area's heating-up temperature is 268 DEG C, Two area's heating-up temperatures are 300 DEG C, three-zone heating temperature is 298 DEG C, and four area's heating-up temperatures are 298 DEG C, and five area's heating-up temperatures are 282 DEG C, six area's heating-up temperatures are 268 DEG C, and spinning body temperature is 265 DEG C；

Embodiment nine (514 monofilament of polyamide)

In the present embodiment, it is the polyamide 514 in preparation example eight except adjusting polyamide 511 in embodiment six, other and enforcement Example six is similarly operated, and is comprised the following steps that：

(1) the section 20kg of polyamide 514 in preparation example eight, is taken, after being dried, is continuously fed in single-screw extrusion machine, Jing adds Heat, extrude, be melt into 511 fused mass of polyamide, single screw extrusion machine zonal control vertically, area's heating-up temperature is 268 DEG C, Two area's heating-up temperatures are 300 DEG C, three-zone heating temperature is 298 DEG C, and four area's heating-up temperatures are 298 DEG C, and five area's heating-up temperatures are 282 DEG C, six area's heating-up temperatures are 268 DEG C, and spinning body temperature is 265 DEG C；

Embodiment ten (516 monofilament of polyamide)

In the present embodiment, it is the polyamide 516 in preparation example nine except adjusting polyamide 511 in embodiment six, other and enforcement Example six is similarly operated, and is comprised the following steps that：

(1) the section 20kg of polyamide 516 in preparation example nine, is taken, after being dried, is continuously fed in single-screw extrusion machine, Jing adds Heat, extrude, be melt into 511 fused mass of polyamide, single screw extrusion machine zonal control vertically, area's heating-up temperature is 268 DEG C, Two area's heating-up temperatures are 300 DEG C, three-zone heating temperature is 298 DEG C, and four area's heating-up temperatures are 298 DEG C, and five area's heating-up temperatures are 282 DEG C, six area's heating-up temperatures are 268 DEG C, and spinning body temperature is 265 DEG C；

Embodiment 11 (518 monofilament of polyamide)

In the present embodiment, it is the polyamide 518 in preparation example ten except adjusting polyamide 511 in embodiment six, other and enforcement Example six is similarly operated, and is comprised the following steps that：

(1) the section 20kg of polyamide 518 in preparation example ten, is taken, after being dried, is continuously fed in single-screw extrusion machine, Jing adds Heat, extrude, be melt into 511 fused mass of polyamide, single screw extrusion machine zonal control vertically, area's heating-up temperature is 268 DEG C, Two area's heating-up temperatures are 300 DEG C, three-zone heating temperature is 298 DEG C, and four area's heating-up temperatures are 298 DEG C, and five area's heating-up temperatures are 282 DEG C, six area's heating-up temperatures are 268 DEG C, and spinning body temperature is 265 DEG C；

Comparative example one

This comparative example provides a kind of preparation method of polyamide 66 monofilament, and which comprises the steps：

(1) the polyamide 66 section 20kg compared in preparation example one, is taken, after being dried, is continuously fed in single-screw extrusion machine, It is heated, extrude, be melt into polyamide 66 fused mass, single screw extrusion machine zonal control vertically, area's heating-up temperature is 280 DEG C, two area's heating-up temperatures be 298 DEG C, three-zone heating temperature be 300 DEG C, four area's heating-up temperatures be 305 DEG C, 5th area heating Temperature is 295 DEG C, and six area's heating-up temperatures are 292 DEG C, and spinning body temperature is 285 DEG C；

(2) long tubes such as, the spinning pump accurate measurement by polyamide 66 fused mass Jing melt distribution pipes in spinning manifold, Jing Polyamide 66 fused mass (melt) is evenly distributed in filament spinning component, the melt mixed in filament spinning component is from filament spinning component Circular spinneret (hole count the is 44 holes) high pressure of bottom sprays to form filament；

(3), filament falls into cooling shaping in 33 DEG C of water-baths, is carried out after entering nearly boiling water bath (about 85 DEG C) Jing after one drawing-off Two road drawing-offs, twice draw ratio are controlled 3.8, are then wound in square circle, carry out heat in being transferred to 110 DEG C of steam coppers after full volume Sizing 0.5 hour, is finally transferred to 50 DEG C, polyamide 66 monofilament is dried to obtain in drying room.

Comparative example two

This comparative example provides a kind of preparation method of polyamide 612 monofilament, and which comprises the steps：

(1) the polyamide 612 section 20kg compared in preparation example two, is taken, after being dried, is continuously fed in single-screw extrusion machine, It is heated, extrude, be melt into polyamide 612 fused mass, single screw extrusion machine zonal control vertically, area's heating-up temperature is 275 DEG C, two area's heating-up temperatures be 302 DEG C, three-zone heating temperature be 302 DEG C, four area's heating-up temperatures be 302 DEG C, 5th area heating Temperature is 285 DEG C, and six area's heating-up temperatures are 272 DEG C, and spinning body temperature is 268 DEG C；

(2), the spinning pump accurate measurement by polyamide 612 fused mass Jing melt distribution pipes in spinning manifold, Jing are isometric Pipe is evenly distributed to polyamide 612 fused mass (melt) in filament spinning component, and the melt mixed in filament spinning component is from spinning Circular spinneret (hole count the is 44 holes) high pressure of component bottom sprays to form filament；

(3), filament falls into cooling shaping in 33 DEG C of water-baths, is carried out after entering nearly boiling water bath (about 85 DEG C) Jing after one drawing-off Two road drawing-offs, twice draw ratio are controlled 3.8, are then wound in square circle, carry out heat in being transferred to 110 DEG C of steam coppers after full volume Sizing 0.5 hour, is finally transferred to 50 DEG C, polyamide 612 monofilament is dried to obtain in drying room.

Embodiment one is as shown in table 4 to the technological parameter of embodiment 11 and the preparation method of comparative example one to two.Embodiment one Property to the polyamide monofilament obtained by embodiment 11 and comparative example one to comparative example two is as shown in table 5.

Table 4 is embodiment one to embodiment ten and the process parameter table of the preparation method of comparative example one and comparative example two

Table 5 is the property list of the polyamide monofilament obtained by embodiment one to embodiment ten

As seen from the above table, obtained by various embodiments of the present invention at the beginning of polyamide monofilament (with odd numbers of carbon atoms monomer as raw materials for production) Beginning modulus is less than traditional polyamide 66 monofilament and polyamide 612 monofilament (with even-numbered carbon atom monomer as raw materials for production) and curved Bent rebound degree is higher than traditional polyamide 66 monofilament and polyamide 612 monofilament, illustrates the polyamide list obtained by various embodiments of the present invention Silk not only has good pliability, and has preferably lodging resistance, low initial modulus and height can needed to flex back to The field application of bullet rate.

The above-mentioned description to embodiment is to be understood that for ease of those skilled in the art and use the present invention.It is familiar with The personnel of art technology obviously easily can make various modifications to these embodiments, and should General Principle described herein Use in other embodiment without through performing creative labour.Therefore, the invention is not restricted to above-described embodiment, art technology Personnel's announcement of the invention, the improvement made without departing from scope and modification all should be in protection scope of the present invention Within.

Claims

1. a kind of polyamide monofilament, it is characterised in that：Its raw materials for production at least contains polyamide, the production of the polyamide Raw material at least contains 1,5- pentanediamines.

2. polyamide monofilament according to claim 1, it is characterised in that：The raw materials for production of the polyamide monofilament contain other groups Into polymer and/or auxiliary agent；And/or, the raw materials for production of the polyamide contain aliphatic long carbochain biatomic acid；And/or, institute The raw materials for production for stating polyamide contain additive；

Preferably, the number of the carbon atom of the aliphatic long carbochain biatomic acid is 10～18.

3. polyamide monofilament according to claim 1, it is characterised in that：The polyamide contains polyamide, the polyamides Amine is selected from polyamide 510, polyamide 511, polyamide 512, polyamide 513, polyamide 514, polyamide 516 and polyamide Any one or a few in 518；

Preferably, the addition of the polyamide is not less than the 50% of the polyamide gross weight；And/or, the additive Addition less than the polyamide gross weight 50%.

It is highly preferred that the addition of the polyamide is not less than the 70% of the polyamide gross weight；And/or, the addition The addition of agent less than the polyamide gross weight 30%.

4. according to the arbitrary described polyamide monofilament of claims 1 to 3, it is characterised in that：The viscosity number of the polyamide be 100～ 400mL/g；And/or, the terminal amino group content of the polyamide is 5～100mol/ton；

Preferably, the viscosity number of the polyamide is 120～240mL/g；And/or, the terminal amino group content of the polyamide For 10～70mol/ton；

It is highly preferred that the viscosity number of the polyamide is 130～200mL/g；And/or, the Amino End Group of the polyamide contains Measure as 20～60mol/ton；

Most preferably, the viscosity number of the polyamide is 135～180mL/g.

5. according to the arbitrary described polyamide monofilament of claims 1 to 3, it is characterised in that：The initial modulus of the polyamide monofilament is 1400～4200MPa；And/or, bending springback rate >=50% of the polyamide monofilament；And/or, the polyamide monofilament it is straight Footpath is 0.1～3.0mm；And/or, the fracture strength >=4.5N of the polyamide monofilament；And/or, the fracture of the polyamide monofilament Elongation is 10～63%；

Preferably, the initial modulus of the polyamide monofilament is 2000～3800MPa；And/or, the bending of the polyamide monofilament Rebound degree >=60%；And/or, the fracture strength >=8N of the polyamide monofilament；And/or, the extension at break of the polyamide monofilament Rate is 18～55%；

It is highly preferred that the initial modulus of the polyamide monofilament is 2600～3500MPa；And/or, the polyamide monofilament it is curved Bent rebound degree >=65%.

6. a kind of preparation method of the polyamide monofilament as described in arbitrary in claim 1 to 5, it is characterised in that：Comprise the steps： By dried polyamide through spinneret operation, cooling shaping, drafting process and winding sizing, polyamide monofilament is obtained.

7. preparation method according to claim 6, it is characterised in that：The preparation side of the polyamide contained by the polyamide Method comprises the steps：

The polyamide salt aqueous solution is heated up under conditions of pH value is for 7.5～8.9 in polymeric kettle, when the pressure in polymeric kettle reaches 0.2～2.0Mpa starts exhaust, when temperature reaches 220～290 DEG C is evacuated to 0～-0.1Mpa, maintain the vacuum 0～ 60min, obtains the polyamide.

8. preparation method according to claim 6, it is characterised in that：The drafting process includes at least twice drafting process, the The ratio of two road drawing-offs and first drawing-off is 2～7.

9. according to arbitrary described preparation method in claim 6 to 8, it is characterised in that：The spinneret operation comprises the steps： The dried polyamide sliced, heating, melting and filament spinning component will be sent into after extruding, high pressure spinneret is forming fiber Silk.

10. application of the polyamide monofilament as described in arbitrary in claim 1 to 5 in the brush filament for preparing washing and brushing apparatus；

Preferably, the washing and brushing apparatus are toothbrush or ecouvillon；

It is highly preferred that a diameter of 0.15～0.35mm per brush filament described in root.

A kind of 11. washing and brushing apparatus, it is characterised in that：Polyamide list as described in brush filament on its brush is arbitrary in such as claim 1 to 5 Silk is made；

Preferably, the washing and brushing apparatus are toothbrush or ecouvillon；