CN118165506A - Nylon 12 composition and preparation method thereof - Google Patents
Nylon 12 composition and preparation method thereof Download PDFInfo
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- CN118165506A CN118165506A CN202410354948.0A CN202410354948A CN118165506A CN 118165506 A CN118165506 A CN 118165506A CN 202410354948 A CN202410354948 A CN 202410354948A CN 118165506 A CN118165506 A CN 118165506A
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- 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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Abstract
The invention discloses a nylon 12 composition and a preparation method thereof, wherein the nylon 12 composition comprises the following components in parts by weight: 100 parts of nylon 12 resin; 1-10 parts of amphiphilic branched block copolymer; 0.2-0.5 part of lubricant; 0.2-0.5 part of antioxidant. The amphiphilic branched segmented copolymer used in the invention is prepared by esterification reaction of carboxyl end-capped branched nylon 12 and monohydroxy end-capped polyurethane elastomer oligomer. The amphiphilic branched block copolymer can effectively improve the compatibility of nylon 12 and polyurethane elastomer, realize the effective adhesion of the nylon 12 and the polyurethane elastomer, and can be applied to the fields of double-color injection molding and cladding processing related to the adhesion of the nylon 12 and the polyurethane elastomer.
Description
Technical Field
The invention relates to the field of polymer bonding modification, in particular to a nylon 12 composition easy to bond with polyurethane elastomer.
Background
The polyurethane elastomer has the high elastic property and soft touch of the traditional rubber, and has the melt processing property of general plastic, and can be often bonded with other plastic materials for use in practical application, for example, nylon 12 is prepared by adopting a double-color injection molding process to be used as a sole support piece, and the polyurethane elastomer is used as a cladding piece to be applied to the field of high-end running shoes.
However, due to the large difference in chemical structures between nylon 12 and polyurethane elastomer, the poor compatibility, the interfacial adhesion performance between the two-shot molding nylon 12 and polyurethane elastomer is often poor, so that tearing and damage are easy to occur in the use process. The addition of a compatibilizer is an effective way to improve the compatibility of incompatible materials, and the patent CN103554819A, CN104387753a adopts maleic anhydride grafted modified polyolefin as the compatibilizer to improve the compatibility of nylon and polyurethane elastomer and improve the coating interface bonding performance of the elastomer to nylon. Patent CN105255158a utilizes the diisocyanate-terminated oligomer as a reactive compatibilizer to improve the compatibility of polyurethane elastomers with long chain nylons.
The scheme can improve the bonding performance of nylon and polyurethane elastomer to a certain extent, but with further improvement of the safety requirement of consumers, the scheme needs to be further optimized.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a nylon 12 composition. The invention prepares a polymer similar to the nylon 12 and polyurethane elastomer in structure, the polymer has good compatibility with both the nylon 12 and polyurethane elastomer, and the nylon 12 composition with good adhesion with polyurethane elastomer can be prepared by adding the polymer serving as a compatilizer into nylon 12.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a nylon 12 composition comprises the following components in parts by weight: 100 parts of nylon 12 resin; 1-10 parts of amphiphilic branched block copolymer; 0.2-0.5 part of lubricant; 0.2-0.5 part of antioxidant.
The nylon 12 composition of the present invention is easily bonded to polyurethane elastomers.
In some examples, the method of making the nylon 12 composition comprises the steps of:
(1) Raw material mixing: adding nylon 12 resin, amphiphilic branched block copolymer, lubricant and antioxidant into a high-speed stirrer, and mixing for 10-30min to obtain a nylon 12 mixed material;
(2) The preparation method of the nylon 12 composition granules comprises the following steps: and (3) melting and extruding the nylon 12 mixture prepared in the step (1) through a double-screw extruder, water-cooling, granulating and drying.
In some examples, the nylon 12 resin has a relative viscosity of 1.50 to 2.50 (m-cresol as solvent, 0.005g/ml concentration), preferably 1.60 to 2.20.
In some examples, the method of preparing the amphiphilic branched block copolymer comprises the steps of:
(1) Preparation of monohydroxy terminated polyurethane elastomer oligomer:
Respectively heating polyether glycol and a monohydroxy end capping agent to 100-120 ℃ and dehydrating for 1-4 hours under the vacuum degree of-90 kPa for standby;
Adding a certain proportion of dehydrated polyether glycol, diisocyanate and monohydroxy blocking agent into a reaction kettle, heating to 80-90 ℃ for reaction for 1-3h, and cooling to obtain monohydroxy blocked polyurethane elastomer oligomer;
preferably, the polyether glycol is selected from one or more of polyethylene glycol, polypropylene glycol and polytetramethylene glycol, and has a number average molecular weight of 400-1000;
preferably, the diisocyanate is selected from one or more of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), 1, 5-Naphthalene Diisocyanate (NDI), hexamethylene Diisocyanate (HDI), isoparaffin diisocyanate (IPDI);
Preferably, the molar ratio of polyether glycol to diisocyanate is 1:1, a step of;
preferably, the number average molecular weight of the monohydroxy terminated polyurethane elastomer oligomer is 800 to 5000, more preferably 1000 to 3000;
preferably, the monohydroxy terminated polyurethane elastomer oligomer has a hydroxyl terminated content of 0.2 to 1.25mmol/g, more preferably 0.33 to 1mmol/g;
preferably, the monohydroxy end-capping agent is selected from one or more of n-butanol, 1-pentanol, 1-heptanol and benzyl alcohol, and the feeding amount is determined by the number average molecular weight of the monohydroxy end-capped polyurethane elastomer oligomer;
(2) Carboxyl end-capped branched nylon 12 preparation:
Adding a certain proportion of laurolactam, dibasic acid end-capping agent, catalyst and water into a reaction kettle, heating to raise the temperature for reaction (in some examples, raising the temperature to 240-290 ℃ for 2-6 h); after the reaction is completed, pressure is released (in some examples, the pressure is released to 5-10 kPa), the temperature is reduced (in some examples, the temperature is reduced to 220-240 ℃), then vacuum treatment is carried out (in some examples, the vacuum is carried out to-90 kPa for 1-3 hours), and the melt polycondensation is completed to prepare the dicarboxyl end-capped nylon 12 oligomer;
After melt polycondensation is completed, adding a certain proportion of polyamine branching agent, continuing vacuum reaction (in some examples, maintaining-90 kPa vacuum reaction for 0.5-1 h), adding nitrogen (in some examples, adding nitrogen to 100-300 kPa), and cooling (in some examples, cooling to 20-30 ℃) to obtain carboxyl end-capped branched nylon 12;
in some examples, the dibasic acid blocking agent in the step (2) is selected from one or more of adipic acid, sebacic acid and dodecanedioic acid, and the adding amount is 3-15% of the mass of the dodecalactam.
In some examples, the catalyst is at least one of phosphoric acid, hypophosphorous acid, sodium hypophosphite, preferably added in an amount of 0.005-0.02% by mass of nylon monomer;
in some examples, the water is ultrapure water added in an amount of 5-15% of the dodecalactam mass;
in some examples, the polyamine branching agent is selected from one or more of 1,3, 5-benzene triamine, 1,2,4, 5-benzene tetramine, 1,2,3,4, 5-benzene pentamine, 1,2,3,4,5, 6-benzene hexamine.
In some examples, the molar ratio of polyamine branching agent amino content to dibasic acid capping agent is 1:1.
In some examples, the carboxyl-terminated branched nylon 12 has a number average molecular weight of 3000-30000, more preferably 8000-15000.
(3) Preparation of amphiphilic branched block copolymer:
Adding a certain proportion of the monohydroxy terminated polyurethane elastomer oligomer prepared in the step (1) and an esterification catalyst into a reaction kettle filled with carboxyl terminated branched nylon 12, heating (in some examples, heating to 220-240 ℃), vacuumizing (in some examples, vacuumizing to reduce the absolute pressure of a reaction system to below 1 kPa), continuing the reaction (in some examples, reacting for 1-3 hours) to obtain an amphiphilic branched block copolymer, and then carrying out traction, water cooling and granulating to obtain amphiphilic branched block copolymer granules.
In some examples, it is desirable to ensure that the molar ratio of hydroxyl content of the monohydroxy terminated polyurethane elastomer oligomer in step (3) to the diacid endcapping agent in step (2) is 1:1, a step of;
In some examples, the esterification catalyst is selected from one or more of tetrabutyl titanate, tetraisopropyl titanate and dioctyltin oxide, and the addition amount is 0.5-2 per mill of the mass of the monohydroxy terminated polyurethane elastomer oligomer.
In some examples, the amphiphilic branched block copolymer has a number average molecular weight of 5000-60000, more preferably 10000-40000;
in some examples, the lubricant is selected from one or more of Ethylene Bis Stearamide (EBS), oleamide, silicone oil, paraffin wax, preferably Ethylene Bis Stearamide (EBS).
In some examples, the antioxidant is selected from one or more of antioxidant 1010, antioxidant 1098, antioxidant 168 and antioxidant H10, preferably a compound system of antioxidant 1010 and antioxidant 1681:2.
Compared with the prior art, the invention has the main advantages that: according to the invention, firstly, a carboxyl end-capped branched nylon 12 is prepared by reacting a dicarboxyl end-capped nylon 12 oligomer with polyamine by utilizing an amidation reaction mechanism, and then, the carboxyl end-capped branched nylon 12 and a monohydroxy end-capped polyurethane elastomer oligomer are subjected to an esterification reaction by utilizing an esterification reaction mechanism to prepare a branched block copolymer of the nylon 12 and the polyurethane elastomer, wherein the branched block copolymer can effectively improve the compatibility of the polyurethane elastomer and the nylon 12, so that the bonding performance of the polyurethane elastomer and the nylon 12 is improved, and the method can be applied to the fields of double-color injection molding and cladding processing of the nylon 12 and the polyurethane elastomer, and can be popularized to any field of blending modification containing the nylon and the polyurethane elastomer.
Drawings
FIG. 1 is a schematic view of a bond strength test specimen.
Detailed Description
The invention will now be further illustrated by means of specific examples which are given solely by way of illustration of the invention and do not limit the scope thereof.
The testing method comprises the following steps:
(1) Number average molecular weight test: the test was performed by a Gel Permeation Chromatography (GPC) system, equipment model number WATERS1515;
(2) Terminal hydroxyl group content test: the test was performed by potentiometric titration (Metrohm 848 automatic potentiometric titration);
(3) And (3) adhesive strength test: firstly, a nylon 12 composition is subjected to injection molding to form a tensile test sample (ISO 527 standard sample), a cutter is used for cutting the sample in the middle, half of the sample is put into a mould again, polyurethane elastomer to be bonded is continuously subjected to injection molding to prepare a bonding strength test sample, and tensile property test is carried out according to ISO 527 test standard.
[ Preparation example 1]
The monohydroxy terminated polyurethane elastomer oligomer was prepared for use according to the following procedure
(1) Polyethylene glycol (mn=400, beijing enokagaku technology limited) and n-butanol (99.9% (GC), beijing enokagaku technology limited) were heated to 100 ℃ respectively and dehydrated at vacuum-90 kPa for 4 hours;
(2) 10kg of dehydrated polyethylene glycol, 4.354kg of toluene diisocyanate (TDI, wanhua chemistry) and 900g of dehydrated n-butanol are added into a reaction kettle, nitrogen is replaced for five times, the temperature is raised to 80 ℃ for reaction for 1h, and the monohydroxy terminated polyurethane elastomer oligomer (TPU-1) is obtained through water cooling. The number average molecular weight of the prepared monohydroxy terminated polyurethane elastomer oligomer was 1010, and the hydroxyl terminated content was 0.990mmol/g.
[ Preparation example 2]
The monohydroxy terminated polyurethane elastomer oligomer was prepared for use according to the following procedure
(1) Polypropylene glycol (mn=600, beijing enoki technology limited) and 1-pentanol (99.9% (GC), beijing enoki technology limited) were heated to 110 ℃ respectively and dehydrated at vacuum level-90 kPa for 2 hours;
(2) 10kg of dehydrated polypropylene glycol, 4.171kg of diphenylmethane diisocyanate (MDI, wanhua chemical) and 600g of dehydrated 1-pentanol are added into a reaction kettle, nitrogen is replaced for five times, the mixture is heated to 85 ℃ for reaction for 2 hours, and the monohydroxy terminated polyurethane elastomer oligomer (TPU-2) is obtained through water cooling. The number average molecular weight of the prepared monohydroxy terminated polyurethane elastomer oligomer is 2120, and the hydroxyl terminated content is 0.472mmol/g.
[ Preparation example 3]
The monohydroxy terminated polyurethane elastomer oligomer was prepared for use according to the following procedure
(1) Polytetramethylene glycol (Mn=600, beijing enoki technology Co., ltd.) and 1-heptanol (99.9% (GC), beijing enoki technology Co., ltd.) were heated to 110℃respectively, and dehydrated under vacuum degree-90 kPa for 2 hours;
(2) 10kg of dehydrated polytetramethylene glycol, 2.803kg of hexamethylene diisocyanate (HDI, wanhua chemical) and 500g of dehydrated 1-heptanol are added into a reaction kettle, nitrogen is replaced for five times, the temperature is raised to 85 ℃ for reaction for 2 hours, and the monohydroxy terminated polyurethane elastomer oligomer (TPU-3) is obtained through water cooling. The number average molecular weight of the prepared monohydroxy terminated polyurethane elastomer oligomer is 3050, and the content of hydroxyl end groups is 0.328mmol/g.
[ PREPARATION EXAMPLE 4]
The monohydroxy terminated polyurethane elastomer oligomer was prepared for use according to the following procedure
(1) Polyethylene glycol (mn=1000, beijing enokic technologies limited) and benzyl alcohol (99.9% (GC), respectively, were heated to 120 ℃ and dehydrated at-90 kPa for 3 hours under vacuum;
(2) 10kg of dehydrated polyethylene glycol, 1.742kg of toluene diisocyanate (TDI, wanhua chemistry) and 270g of dehydrated benzyl alcohol are added into a reaction kettle, nitrogen is replaced for five times, the mixture is heated to 90 ℃ for reaction for 3 hours, and the monohydroxy terminated polyurethane elastomer oligomer (TPU-4) is obtained through water cooling. The number average molecular weight of the prepared monohydroxy terminated polyurethane elastomer oligomer was 4750, and the hydroxyl terminated content was 0.211mmol/g.
[ Preparation example 5]
The carboxyl-terminated branched nylon 12 was prepared according to the following procedure
Adding 2kg of laurolactam, 300g of adipic acid, 0.1g of phosphoric acid and 100g of ultrapure water into a reaction kettle, replacing nitrogen for five times, heating to 280 ℃ and maintaining for 5 hours to complete the ring-opening reaction of the laurolactam; after the ring opening is completed, the pressure is released to 10kPa, the temperature is reduced to 230 ℃ at the same time, and then the vacuum pumping treatment is carried out for 120min, thus completing the melt polycondensation; after completion of melt polycondensation, 518g of 1,2,3,4,5, 6-benzene hexamine was added, vacuum reaction was continued for 1 hour, vacuum was stopped, nitrogen was added to 100kpa, stirring was stopped and cooling to 30 ℃ was performed to obtain carboxyl terminated branched nylon 12 (BPA-1). The carboxyl-terminated branched nylon 12 prepared had a number average molecular weight of 6810.
[ Preparation example 6]
The carboxyl-terminated branched nylon 12 was prepared according to the following procedure
Adding 2kg of laurolactam, 200g of sebacic acid, 0.2g of hypophosphorous acid and 200g of ultrapure water into a reaction kettle, replacing nitrogen for five times, heating to 280 ℃ and maintaining for 5 hours to complete the ring-opening reaction of the laurolactam; after the ring opening is completed, the pressure is released to 10kPa, the temperature is reduced to 230 ℃ at the same time, and then the vacuum pumping treatment is carried out for 120min, thus completing the melt polycondensation; after the melt polycondensation was completed, 173g of 1,2,4, 5-benzenetetramine was added, the vacuum reaction was continued for 1 hour, the vacuum was stopped, nitrogen was added to 100kpa, stirring was stopped and the temperature was lowered to 30 ℃ to obtain carboxyl terminated branched nylon 12 (BPA-2). The number average molecular weight of the prepared carboxyl end-capped branched nylon 12 is 8950.
[ Preparation example 7]
The carboxyl-terminated branched nylon 12 was prepared according to the following procedure
2Kg of laurolactam, 150g of dodecanedioic acid, 0.4g of hypophosphorous acid and 300g of ultrapure water are added into a reaction kettle, nitrogen is replaced for five times, and the mixture is heated to 280 ℃ and kept for 5 hours to complete the ring-opening reaction of the laurolactam; after the ring opening is completed, the pressure is released to 10kPa, the temperature is reduced to 230 ℃ at the same time, and then the vacuum pumping treatment is carried out for 120min, thus completing the melt polycondensation; after the melt polycondensation was completed, 80g of 1,3, 5-benzene triamine was added, the vacuum reaction was continued for 1 hour, the vacuum was stopped, nitrogen was added to 100kpa, stirring was stopped and the temperature was lowered to 30 ℃ to obtain carboxyl terminated branched nylon 12 (BPA-3). The number average molecular weight of the prepared carboxyl end-capped branched nylon 12 is 9010.
[ Preparation example 8]
The carboxyl-terminated branched nylon 12 was prepared according to the following procedure
Adding 2kg of laurolactam, 60g of adipic acid, 0.1g of hypophosphorous acid and 200g of ultrapure water into a reaction kettle, replacing nitrogen for five times, heating to 280 ℃ and maintaining for 5 hours to complete the ring-opening reaction of the laurolactam; after the ring opening is completed, the pressure is released to 10kPa, the temperature is reduced to 230 ℃ at the same time, and then the vacuum pumping treatment is carried out for 120min, thus completing the melt polycondensation; after completion of melt polycondensation, 104g of 1,2,3,4,5, 6-benzene hexamine was added, vacuum reaction was continued for 1 hour, vacuum was stopped, nitrogen was added to 100kpa, stirring was stopped and the temperature was lowered to 30 ℃ to obtain carboxyl terminated branched nylon 12 (BPA-4). The number average molecular weight of the prepared carboxyl end-capped branched nylon 12 is 29950.
[ Preparation example 9]
The carboxyl-terminated branched nylon 12 was prepared according to the following procedure
Adding 2kg of laurolactam, 300g of adipic acid, 0.1g of hypophosphorous acid and 100g of ultrapure water into a reaction kettle, replacing nitrogen for five times, heating to 280 ℃ and maintaining for 5 hours to complete the ring-opening reaction of the laurolactam; after the ring opening is completed, the pressure is released to 10kPa, the temperature is reduced to 230 ℃ at the same time, and then the vacuum pumping treatment is carried out for 120min, thus completing the melt polycondensation; after the melt polycondensation was completed, 255 g of 1,3, 5-trimellitic amine was added, the vacuum reaction was continued for 1 hour, the vacuum was stopped, nitrogen was added to 100kpa, stirring was stopped and the temperature was lowered to 30 ℃ to obtain carboxyl terminated branched nylon 12 (BPA-5). The number average molecular weight of the prepared carboxyl end-capped branched nylon 12 is 3220.
[ Preparation example 10]
The amphiphilic branched block copolymer pellets are prepared according to the following steps:
To a reaction vessel containing carboxyl-terminated branched nylon 12 (BPA-1, preparation example 5), 2073g of TPU-1 prepared in preparation example 1 and 1.04g of tetrabutyl titanate (Beijing Enoka technology Co., ltd.) were charged, nitrogen was replaced five times, the temperature was raised to 230℃and the absolute pressure of the reaction system was reduced to 80Pa by vacuum pumping, and after continuing the reaction for 2 hours, pellets of an amphiphilic branched block copolymer (TPU-PA-1) having a number average molecular weight of 12680 were produced by traction, water cooling and pelletizing.
[ Preparation example 11 ]
The amphiphilic branched block copolymer pellets are prepared according to the following steps:
9751g of TPU-4 prepared in preparation example 4 and 9.75g of tetraisopropyl titanate (Beijing enoKai technology Co., ltd.) were charged into a reaction vessel containing carboxyl-terminated branched nylon 12 (BPA-1, preparation example 5), nitrogen was replaced five times, heated to 230℃and evacuated to reduce the absolute pressure of the reaction system to 80Pa, and after continuing the reaction for 2 hours, amphiphilic branched block copolymer pellets (TPU-PA-2) were prepared by traction, water cooling and pelletizing, the amphiphilic branched block copolymer pellets having a number average molecular weight of 35150.
[ Preparation example 12 ]
The amphiphilic branched block copolymer pellets are prepared according to the following steps:
Into a reaction vessel containing carboxyl-terminated branched nylon 12 (BPA-4, preparation example 8), 1950g TPU-4 prepared in preparation example 4 and 3.90g dioctyl tin oxide (Beijing Enoka technology Co., ltd.) were charged, nitrogen was replaced five times, heated to 230℃and evacuated to reduce the absolute pressure of the reaction system to 80Pa, and after continuing the reaction for 3 hours, amphiphilic branched block copolymer pellets (TPU-PA-3) were prepared by traction, water cooling and pelletizing, the amphiphilic branched block copolymer having a number average molecular weight of 58150.
[ Preparation example 13 ]
The amphiphilic branched block copolymer pellets are prepared according to the following steps:
2096g of TPU-2 prepared in preparation example 2 and 2.10g of dioctyl tin oxide (Beijing Enoka technology Co., ltd.) were charged into a reaction vessel containing carboxyl end-capped branched nylon 12 (BPA-2, preparation example 6), nitrogen was replaced five times, heated to 230℃and evacuated to reduce the absolute pressure of the reaction system to 80Pa, and after continuing the reaction for 2 hours, pellets of an amphiphilic branched block copolymer (TPU-PA-4) having a number average molecular weight of 17280 were prepared by drawing, water cooling and pelletizing.
[ Preparation example 14 ]
The amphiphilic branched block copolymer pellets are prepared according to the following steps:
A reaction vessel containing carboxyl-terminated branched nylon 12 (BPA-3, preparation example 7) was charged with 1987g of TPU-3 prepared in preparation example 3 and 1.99g of dioctyl tin oxide (Beijing Enoka technology Co., ltd.) and replaced with nitrogen five times, heated to 230℃and evacuated to reduce the absolute pressure of the reaction system to 80Pa, and after continuing the reaction for 2 hours, an amphiphilic branched block copolymer pellet (TPU-PA-5) having a number average molecular weight of 18050 was prepared by drawing, water cooling and pelletizing.
[ Preparation example 15 ]
The amphiphilic branched block copolymer pellets are prepared according to the following steps:
To a reaction vessel containing carboxyl-terminated branched nylon 12 (BPA-5, preparation example 9), 2073g of TPU-1 prepared in preparation example 1 and 2.07g of dioctyl tin oxide (Beijing Enoki technology Co., ltd.) were charged, nitrogen was replaced five times, the temperature was raised to 230℃and the absolute pressure of the reaction system was reduced to 80Pa by vacuum-pumping, and after continuing the reaction for 1 hour, amphiphilic branched block copolymer pellets (TPU-PA-6) were prepared by traction-water cooling-pelletizing, and the amphiphilic branched block copolymer had a number average molecular weight of 6020.
[ Preparation example 16 ]
The amphiphilic branched block copolymer pellets are prepared according to the following steps:
9750g of TPU-4 prepared in preparation example 4 and 9.75g of dioctyl tin oxide (Beijing Enoka technology Co., ltd.) were charged into a reaction vessel containing carboxyl end-capped branched nylon 12 (BPA-5, preparation example 9), nitrogen was replaced five times, the temperature was raised to 230 ℃, the absolute pressure of the reaction system was reduced to 80Pa by vacuum pumping, and after continuing the reaction for 2 hours, amphiphilic branched block copolymer pellets (TPU-PA-7) were prepared by traction-water cooling-pelletizing, and the amphiphilic branched block copolymer had a number average molecular weight of 17360.
[ Example 1]
The nylon 12 composition granules were prepared according to the following steps:
(1) Raw material mixing: 5kg of nylon 12 (Wanhua chemical, L1000, relative viscosity 1.60), 250g of amphiphilic branched block copolymer (TPU-PA-1), 10g of lubricant EBS (Japanese flower king) and 10g of lubricant EBS (equal mass compound of antioxidant 1098 and antioxidant 168, li Anlong New Material Co., ltd.) are added into a high-speed mixer and mixed for 20min to prepare a nylon 12 mixture.
(2) The preparation method of the nylon 12 composition granules comprises the following steps: and (3) carrying out melt extrusion on the nylon mixture prepared in the step (1) by a double-screw extruder with the length-diameter ratio of 42, carrying out water cooling, granulating, and drying to obtain the anti-heat-oxidation aging nylon composition granule, wherein the screw rotating speed is 150rpm, and the temperature from a feeding section to a machine head is set to be 180-220 ℃.
[ Example 2]
The nylon 12 composition granules were prepared according to the following steps:
(1) Raw material mixing: 5kg of nylon 12 (Wanhua chemical, L2000, relative viscosity 1.90), 250g of amphiphilic branched block copolymer (TPU-PA-2), 10g of lubricant EBS (Japanese flower king) and 15g of (equal mass compound of antioxidant 1098 and antioxidant 168, li Anlong New Material Co., ltd.) were added to a high-speed mixer and mixed for 20 minutes to prepare a nylon 12 compound.
(2) The preparation method of the nylon 12 composition granules comprises the following steps: and (3) carrying out melt extrusion on the nylon mixture prepared in the step (1) by a double-screw extruder with the length-diameter ratio of 42, carrying out water cooling, granulating, and drying to obtain the anti-heat-oxidation aging nylon composition granule, wherein the screw rotating speed is 150rpm, and the temperature from a feeding section to a machine head is set to be 180-240 ℃.
[ Example 3]
The nylon 12 composition granules were prepared according to the following steps:
(1) Raw material mixing: 5kg of nylon 12 (Wanhua chemical, L3000, relative viscosity 2.20), 250g of amphiphilic branched block copolymer (TPU-PA-3), 10g of lubricant EBS (Japanese flower king) and 25g of lubricant EBS (equal mass compound of antioxidant 1098 and antioxidant 168, li Anlong New Material Co., ltd.) were added to a high-speed mixer and mixed for 20min to prepare a nylon 12 compound.
(2) The preparation method of the nylon 12 composition granules comprises the following steps: and (3) carrying out melt extrusion on the nylon mixture prepared in the step (1) by a double-screw extruder with the length-diameter ratio of 42, carrying out water cooling, granulating, and drying to obtain the anti-heat-oxidation aging nylon composition granule, wherein the screw rotating speed is 150rpm, and the temperature from a feeding section to a machine head is set to be 180-260 ℃.
[ Example 4]
The nylon 12 composition granules were prepared according to the following steps:
(1) Raw material mixing: 5kg of nylon 12 (Wanhua chemical, L2000, relative viscosity 1.90), 250g of amphiphilic branched block copolymer (TPU-PA-4), 15g of lubricant EBS (Japanese flower king) and 15g of lubricant EBS (equal mass compound of antioxidant 1098 and antioxidant 168, li Anlong New Material Co., ltd.) are added into a high-speed mixer and mixed for 20min to prepare a nylon 12 mixture.
(2) The preparation method of the nylon 12 composition granules comprises the following steps: and (3) carrying out melt extrusion on the nylon mixture prepared in the step (1) by a double-screw extruder with the length-diameter ratio of 42, carrying out water cooling, granulating, and drying to obtain the anti-heat-oxidation aging nylon composition granule, wherein the screw rotating speed is 150rpm, and the temperature from a feeding section to a machine head is set to be 180-240 ℃.
[ Example 5]
The nylon 12 composition granules were prepared according to the following steps:
(1) Raw material mixing: 5kg of nylon 12 (Wanhua chemical, L2000, relative viscosity 1.90), 50g of an amphiphilic branched block copolymer (TPU-PA-5), 25g of lubricant EBS (Japanese flower king) and 15g of an equal mass compound of an antioxidant 1098 and an antioxidant 168 (Li Anlong New Material Co., ltd.) were added to a high-speed mixer and mixed for 20 minutes to prepare a nylon 12 compound.
(2) The preparation method of the nylon 12 composition granules comprises the following steps: and (3) carrying out melt extrusion on the nylon mixture prepared in the step (1) by a double-screw extruder with the length-diameter ratio of 42, carrying out water cooling, granulating, and drying to obtain the anti-heat-oxidation aging nylon composition granule, wherein the screw rotating speed is 150rpm, and the temperature from a feeding section to a machine head is set to be 180-240 ℃.
[ Example 6]
The nylon 12 composition granules were prepared according to the following steps:
(1) Raw material mixing: 5kg of nylon 12 (Wanhua chemical, L2000, relative viscosity 1.90), 250g of amphiphilic branched block copolymer (TPU-PA-6), 15g of lubricant EBS (Japanese flower king) and 15g of lubricant EBS (equal mass compound of antioxidant 1098 and antioxidant 168, li Anlong New Material Co., ltd.) are added into a high-speed mixer and mixed for 20min to prepare a nylon 12 mixture.
(2) The preparation method of the nylon 12 composition granules comprises the following steps: and (3) carrying out melt extrusion on the nylon mixture prepared in the step (1) by a double-screw extruder with the length-diameter ratio of 42, carrying out water cooling, granulating, and drying to obtain the anti-heat-oxidation aging nylon composition granule, wherein the screw rotating speed is 150rpm, and the temperature from a feeding section to a machine head is set to be 180-240 ℃.
[ Example 7]
The nylon 12 composition granules were prepared according to the following steps:
(1) Raw material mixing: 5kg of nylon 12 (Wanhua chemical, L2000, relative viscosity 1.90), 500g of amphiphilic branched block copolymer (TPU-PA-7), 15g of lubricant EBS (Japanese flower king) and 15g of lubricant EBS (equal mass compound of antioxidant 1098 and antioxidant 168, li Anlong New Material Co., ltd.) are added into a high-speed mixer and mixed for 20min to prepare a nylon 12 mixture.
(2) The preparation method of the nylon 12 composition granules comprises the following steps: and (3) carrying out melt extrusion on the nylon mixture prepared in the step (1) by a double-screw extruder with the length-diameter ratio of 42, carrying out water cooling, granulating, and drying to obtain the anti-heat-oxidation aging nylon composition granule, wherein the screw rotating speed is 150rpm, and the temperature from a feeding section to a machine head is set to be 180-240 ℃.
Comparative example 1
The nylon 12 composition granules were prepared according to the following steps:
(1) Raw material mixing: 5kg of nylon 12 (Wanhua chemical, L2000, relative viscosity 1.90), 15g of lubricant EBS (Japanese flower king) and 15g of (equal mass compound of antioxidant 1098 and antioxidant 168, li Anlong New Material Co., ltd.) were added to a high-speed mixer and mixed for 20 minutes to prepare a nylon 12 blend.
(2) The preparation method of the nylon 12 composition granules comprises the following steps: and (3) carrying out melt extrusion on the nylon mixture prepared in the step (1) by a double-screw extruder with the length-diameter ratio of 42, carrying out water cooling, granulating, and drying to obtain the anti-heat-oxidation aging nylon composition granule, wherein the screw rotating speed is 150rpm, and the temperature from a feeding section to a machine head is set to be 180-240 ℃.
Comparative example 2
The nylon 12 composition granules were prepared according to the following steps:
(1) Raw material mixing: 5kg of nylon 12 (Wanhua chemical, L2000, relative viscosity 1.90), 250g of grafted maleic anhydride POE (Dow, N493), 15g of lubricant EBS (Japanese flower king) and 15g of lubricant (equal mass compound of antioxidant 1098 and antioxidant 168, li Anlong New Material Co., ltd.) were added to a high-speed mixer and mixed for 20 minutes to prepare a nylon 12 compound.
(2) The preparation method of the nylon 12 composition granules comprises the following steps: and (3) carrying out melt extrusion on the nylon mixture prepared in the step (1) by a double-screw extruder with the length-diameter ratio of 42, carrying out water cooling, granulating, and drying to obtain the anti-heat-oxidation aging nylon composition granule, wherein the screw rotating speed is 150rpm, and the temperature from a feeding section to a machine head is set to be 180-240 ℃.
The adhesion strength to polyurethane elastomer WHT-8190 was measured according to the adhesion strength test method for each of the examples and comparative examples, and the test results are shown in Table 1:
Table 1, results of the adhesive strength test of the nylon 12 composition prepared in each example and comparative example with polyurethane elastomer
As can be seen from the bonding strength test result data of the examples and the comparative examples in the table 1, the amphiphilic branched block copolymer prepared by the invention can effectively improve the bonding strength of nylon 12 and polyurethane elastomer, effectively avoid cracking of the bonding interface of the product during working, prolong the service life of the product and improve the use safety of the product.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and additions may be made to those skilled in the art without departing from the method of the present invention, which modifications and additions are also to be considered as within the scope of the present invention.
Claims (10)
1. A nylon 12 composition comprises the following components in parts by weight: 100 parts of nylon 12 resin; 1-10 parts of amphiphilic branched block copolymer; 0.2-0.5 part of lubricant; 0.2-0.5 part of antioxidant.
2. A process for preparing the nylon 12 composition of claim 1 comprising the steps of:
(1) Raw material mixing: adding nylon 12 resin, amphiphilic branched block copolymer, lubricant and antioxidant into a high-speed stirrer, and mixing for 10-30min to obtain a nylon 12 mixed material;
(2) The preparation method of the nylon 12 composition granules comprises the following steps: and (3) melting and extruding the nylon 12 mixture prepared in the step (1) through a double-screw extruder, water-cooling, granulating and drying.
3. Nylon 12 composition according to claim 1, characterized in that the nylon 12 resin has a relative viscosity of 1.50-2.50 under test conditions of m-cresol as solvent, a concentration of 0.005g/ml, preferably 1.60-2.20.
4. A nylon 12 composition according to any of claims 1-3, characterized in that the method of preparing the amphiphilic branched block copolymer comprises the steps of:
(a) Preparation of monohydroxy terminated polyurethane elastomer oligomer:
Respectively heating polyether glycol and a monohydroxy end capping agent under vacuum condition for dehydration for later use;
Adding a certain proportion of dehydrated polyether glycol, diisocyanate and dehydrated monohydroxy blocking agent into a reaction kettle, heating to react, and cooling to obtain monohydroxy blocked polyurethane elastomer oligomer;
(b) Carboxyl end-capped branched nylon 12 preparation:
Adding a certain proportion of laurolactam, dibasic acid end-capping agent, catalyst and water into a reaction kettle, and heating to raise the temperature for reaction; after the reaction is finished, pressure relief and temperature reduction are carried out, and then vacuum pumping treatment is carried out, so that the preparation of the dicarboxyl end-capped nylon 12 oligomer through melt polycondensation is finished;
After melt polycondensation is completed, adding a polyamine branching agent with a certain proportion, continuing vacuum reaction, supplementing nitrogen, and cooling to obtain carboxyl end-capped branched nylon 12;
(c) Preparation of amphiphilic branched block copolymer:
And (2) adding a certain proportion of the monohydroxy terminated polyurethane elastomer oligomer prepared in the step (a) and an esterification catalyst into a reaction kettle filled with carboxyl terminated branched nylon 12, heating, vacuumizing, continuing to react to obtain an amphiphilic branched block copolymer, and then carrying out traction, water cooling and granulating to obtain amphiphilic branched block copolymer granules.
5. The nylon 12 composition of claim 4 wherein in step (a), the polyether glycol is selected from one or more of polyethylene glycol, polypropylene glycol and polytetramethylene glycol and has a number average molecular weight of 400 to 1000;
The diisocyanate is selected from one or more of toluene diisocyanate, diphenylmethane diisocyanate, 1, 5-naphthalene diisocyanate, hexamethylene diisocyanate and isoparaffin diisocyanate;
the molar ratio of the polyether glycol to the diisocyanate is 1:1, a step of;
The number average molecular weight of the monohydroxy terminated polyurethane elastomer oligomer is 800 to 5000, more preferably 1000 to 3000;
the hydroxyl-terminated polyurethane elastomer oligomer has a hydroxyl-terminated content of 0.2 to 1.25mmol/g, more preferably 0.33 to 1mmol/g;
The monohydroxy end-capping agent is selected from one or more of n-butanol, 1-amyl alcohol, 1-heptanol and benzyl alcohol.
6. The nylon 12 composition of claim 4 wherein the diacid capping agent in step (b) is selected from one or more of adipic acid, sebacic acid, dodecanedioic acid, in an amount of 3-15% of dodecalactam;
The polyamine branching agent is selected from one or more of 1,3, 5-benzene triamine, 1,2,4, 5-benzene tetramine, 1,2,3,4, 5-benzene pentamine and 1,2,3,4,5, 6-benzene hexamine;
preferably, the molar ratio of the amino content of the polyamine branching agent to the dibasic acid end-capping agent is 1:1, a step of;
Preferably, the carboxyl-terminated branched nylon 12 has a number average molecular weight of 3000-30000, more preferably 8000-15000.
7. The nylon 12 composition of claim 4 wherein in step (c) the hydroxyl content of the monohydroxy terminated polyurethane elastomer oligomer to the diacid endcapping agent in step (b) is in a molar ratio of 1:1.
8. Nylon 12 composition according to claim 4, characterized in that the amphiphilic branched block copolymer has a number average molecular weight of 5000-60000, more preferably 10000-40000.
9. The nylon 12 composition of claim 4 wherein the lubricant is selected from one or more of ethylene bis-stearamide, oleamide, silicone oil, paraffin wax, preferably ethylene bis-stearamide.
10. The nylon 12 composition of claim 4, wherein the antioxidant is selected from one or more of antioxidant 1010, antioxidant 1098, antioxidant 168, and antioxidant H10, preferably an antioxidant 1010 and antioxidant 168 1:2 compound system.
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