CN116355401B - Polyamide composition and preparation method and application thereof - Google Patents
Polyamide composition and preparation method and application thereof Download PDFInfo
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- CN116355401B CN116355401B CN202111619186.5A CN202111619186A CN116355401B CN 116355401 B CN116355401 B CN 116355401B CN 202111619186 A CN202111619186 A CN 202111619186A CN 116355401 B CN116355401 B CN 116355401B
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- polyamide composition
- polyethyleneimine
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 92
- 229920002647 polyamide Polymers 0.000 title claims abstract description 92
- 239000000203 mixture Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims description 8
- 229920001971 elastomer Polymers 0.000 claims abstract description 35
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 33
- 239000004593 Epoxy Substances 0.000 claims abstract description 30
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 16
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 14
- 239000000945 filler Substances 0.000 claims description 12
- 239000003365 glass fiber Substances 0.000 claims description 11
- -1 aliphatic diamine Chemical class 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 10
- 239000003822 epoxy resin Substances 0.000 claims description 8
- 229920000647 polyepoxide Polymers 0.000 claims description 8
- 239000004953 Aliphatic polyamide Substances 0.000 claims description 7
- 229920003231 aliphatic polyamide Polymers 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 6
- 230000003078 antioxidant effect Effects 0.000 claims description 6
- 238000006068 polycondensation reaction Methods 0.000 claims description 6
- 229920006152 PA1010 Polymers 0.000 claims description 5
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 5
- 229920006139 poly(hexamethylene adipamide-co-hexamethylene terephthalamide) Polymers 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 229920000305 Nylon 6,10 Polymers 0.000 claims description 4
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- 239000012765 fibrous filler Substances 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 229920006012 semi-aromatic polyamide Polymers 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000000806 elastomer Substances 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 229920001112 grafted polyolefin Polymers 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims description 3
- 239000002667 nucleating agent Substances 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 229920000572 Nylon 6/12 Polymers 0.000 claims description 2
- 229920006121 Polyxylylene adipamide Polymers 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 2
- 150000001413 amino acids Chemical class 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000011324 bead Substances 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 229910052570 clay Inorganic materials 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000003951 lactams Chemical class 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 229920006119 nylon 10T Polymers 0.000 claims description 2
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 claims description 2
- 229920006128 poly(nonamethylene terephthalamide) Polymers 0.000 claims description 2
- 229920006396 polyamide 1012 Polymers 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 239000010456 wollastonite Substances 0.000 claims description 2
- 229910052882 wollastonite Inorganic materials 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 2
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 claims description 2
- 239000002671 adjuvant Substances 0.000 claims 1
- 239000005060 rubber Substances 0.000 abstract description 32
- 230000032683 aging Effects 0.000 abstract description 21
- 239000011248 coating agent Substances 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 6
- 229920001875 Ebonite Polymers 0.000 description 43
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 32
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 32
- 229920002725 thermoplastic elastomer Polymers 0.000 description 29
- 238000012360 testing method Methods 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 16
- 230000000694 effects Effects 0.000 description 10
- 238000005538 encapsulation Methods 0.000 description 9
- 125000003277 amino group Chemical group 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000010073 coating (rubber) Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 2
- 229920006525 PA66-C Polymers 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229920006883 PAMXD6 Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- HVYLDJKDVOOTHV-UHFFFAOYSA-N acetic acid;2-iminoethanethiol Chemical compound CC(O)=O.CC(O)=O.SCC=N HVYLDJKDVOOTHV-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000004148 curcumin Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000000879 imine group Chemical group 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a polyamide composition, which comprises the following components in parts by weight: 100 parts of polyamide with an amino end value of 47-190mmol/kg, 0.0003-0.07 times of epoxy auxiliary agent and 0.0003-0.03 times of polyethyleneimine, wherein the total addition amount of the epoxy auxiliary agent and the polyethyleneimine is not less than 0.1 part. The polyamide composition of the invention has good coating property by soft rubber (TPE, TPV, TPU and the like) and good aging resistance.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a polyamide composition, a preparation method and application thereof.
Background
The modified polyamide has excellent comprehensive properties such as good mechanical properties, chemical resistance and heat resistance, so that the modified polyamide is widely applied to internal stress parts or shell parts and the like in the industries such as rail transit, electric appliances, electric tools, sharing bicycles and the like. Especially when the plastic rubber is used as a shell of an electric tool, a security part and the like, a design that a soft rubber (such as TPE, TPV, TPU and the like) is coated with a hard rubber (reinforced polyamide or filled reinforced polyamide) is often adopted, and the production process is to firstly injection mold a hard rubber part and then coat the soft rubber on the hard rubber through secondary injection molding.
The soft rubber is coated with the hard rubber, so that the hard rubber is protected, and the product has better impact resistance and falling performance, and can bring better hand feeling to users. The soft rubber is coated with the hard rubber, and the critical characteristic is the bonding effect of the soft rubber and the hard rubber, and if the bonding is poor, the abnormality such as degumming and the like can be caused in the using process. The composition and properties of the soft gel play a vital role in the coating effect, and a large number of patents have already described TPE, TPV, TPU materials with good coating effects. In fact, besides the effect of the soft gel, the coating ability of the hard gel part has a great influence on the final coating effect.
At present, with the increasing size, complexity and diversity of product structural designs, the requirements on product performance are gradually improved, and products adopting soft rubber to cover hard rubber designs are gradually increased in various fields, so that the development of polyamide compositions with excellent covering property is needed.
Disclosure of Invention
The present invention aims to provide a polyamide composition which is easily coated with a soft gel.
Another object of the present invention is to provide a process for the preparation and use of the polyamide composition described above.
The invention is realized by the following technical scheme:
A polyamide composition comprises the following components in parts by weight: 100 parts of polyamide with an amino end value of 47-180mmol/kg, 0.0003-0.07 times of epoxy auxiliary agent and 0.0003-0.03 times of polyethyleneimine, wherein the total addition amount of the epoxy auxiliary agent and the polyethyleneimine is not less than 0.1 part.
Preferably, the polyamide has an amino end value of 85 to 120mmol/kg.
The epoxy auxiliary agent is at least one selected from epoxy resin and copolymers containing glycidyl methacrylate monomers; wherein the copolymer containing glycidyl methacrylate monomer is at least one selected from ethylene-butyl acrylate-glycidyl methacrylate copolymer, ethylene-methyl acrylate-glycidyl methacrylate copolymer and ethylene-butyl acrylate-glycidyl methacrylate grafted polyolefin elastomer.
Epoxy resins are preferred.
Specifically, the epoxy resin is bisphenol a type epoxy resin.
The weight average molecular weight of the polyethyleneimine is in the range of 800-2000000; preferably 1300-1000000; more preferably 25000-750000.
Preferably, the content of the epoxy auxiliary agent is 0.003-0.04 times of the total weight of the polyamide, and the content of the polyethyleneimine is 0.003-0.01 times of the total weight of the polyamide.
The polyamide is at least one of aliphatic polyamide or semi-aromatic polyamide, wherein the aliphatic polyamide is polyamide formed by polycondensation of at least one aliphatic dicarboxylic acid and at least one aliphatic diamine and/or polyamide formed by polycondensation of at least one amino acid or at least one lactam and the polyamide, and the polyamide comprises at least one of PA46, PA56, PA510, PA66, PA610, PA612, PA1010, PA1012, PA1212, PA6, PA7, PA11 and PA 12; the semi-aromatic polyamide is formed by polycondensation of at least one aromatic dicarboxylic acid and at least one aliphatic diamine, and is selected from at least one of PA10T, PA T1010, PA10T66, PA MXD6, PA MXD10, PA66/6T, PA6T, PA9T, PA 6T/66;
Preferably, the polyamide is selected from aliphatic polyamides, further preferably at least one of PA6, PA 66.
0-200 Parts of filler; the filler is at least one selected from fibrous filler and granular filler; the fibrous filler is at least one selected from glass fiber and carbon fiber; the granular filler is at least one selected from alumina, carbon black, aluminosilicate clay, montmorillonite, zirconium phosphate, kaolin, calcium carbonate, diatomite, graphite, mica, silica, titanium dioxide, zeolite, talcum powder, wollastonite, glass beads and glass powder. .
Whether 0-3 parts of auxiliary agent is added or not can be determined according to actual requirements, and the auxiliary agent is at least one selected from an antioxidant, a lubricant, a weather-proof agent and a nucleating agent.
The antioxidant can be hindered phenol antioxidant, alkali metal or alkaline earth metal secondary (phosphite) antioxidant, phosphite antioxidant, etc.;
The lubricant may be a higher fatty acid, a higher fatty acid metal salt, a higher fatty acid ester, a higher fatty acid amide, or the like;
The weather-resistant agent can be salicylate, benzotriazole, benzophenone, secondary amine stabilizer, tertiary amine stabilizer, NOR stabilizer, etc.;
The nucleating agent may be a higher fatty acid metal salt, nano-metal particles, or the like.
The preparation method of the polyamide composition comprises the following steps: and (3) uniformly mixing the other components except the filler, feeding the components into a double-screw extruder through a main feeding port for extrusion granulation, wherein the length-diameter ratio of a screw is 36-52:1, the temperature range of a screw barrel is 180-300 ℃, the rotating speed is 200-700rpm, and feeding the components at the filler side to obtain the polyamide composition.
The polyamide composition is applied to preparing soft rubber coated parts, in particular to TPE, TPV, TPU and other soft rubbers.
The invention has the following beneficial effects:
The invention utilizes the synergistic effect of amino groups at the end of nylon Long Shuzhi, epoxy active groups of the epoxy auxiliary agent and high-activity imine groups to react with maleic anhydride in the packaging materials by the synergistic effect of the high-end amino polyamide resin, the epoxy auxiliary agent and the polyethyleneimine, so that the surface activity of the polyamide composition is higher, and the prepared polyamide composition and the conventional soft rubber for polyamide encapsulation have good bonding effect, and can improve the ageing resistance.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
The sources of the raw materials used in the examples and comparative examples are as follows:
PA66-a: terminal amino group content of 47mmol/kg, EP-158, zhejiang Huafeng;
PA66-B: the amino end content is 85mmol/kg, EP158NH, zhejiang Huafeng;
PA66-C: terminal amino group content 110mmol/kg, EP126NH, zhejiang Huafeng;
PA66-D: terminal amino content 180mmol/kg, provided by Zhejiang Huafeng;
PA66-E: terminal amino content 24mmol/kg, EPR32, henan Shenma;
PA6-a: the amino end content is 64mmol/kg, H35ZI and Honiswell;
PA6-B: the amino end content is 23mmol/kg, M2000 and New can Meida.
PA610: the amino end content is 51mmol/kg, PA 610F 120 and Shandong Guangdong boundary.
PA1010: the amino end content is 47mmol/kg, PA1010, no tin Yan Dani Dragon Co., ltd;
PAMXD10: terminal amino content 46mmol/kg, PAMXD10, shanghai solid;
PA66/6T: the content of terminal amino groups is 48mmol/kg, C1504T and Shandong Guangdong boundary; glass fiber: ECS301HP-3-H, CPIC;
talc powder: AH-1250N6, guangxi Longqiang Shenghuamei;
epoxy auxiliary A: epoxy resin, D.E.R. 667-20, dow chemical;
Epoxy auxiliary B: ethylene-butyl acrylate-glycidyl methacrylate copolymer, PTW, duPont U.S.;
Epoxy auxiliary C: ethylene-methyl acrylate-glycerol methacrylate copolymer: AX8900, france alcma;
Epoxy auxiliary D: ethylene-butyl acrylate-glycidyl methacrylate grafted polyolefin elastomer: SOG-03, jiangsu Jia Yi Rong.
Polyethyleneimine a: weight average molecular weight 1300, trade name Lupasol PR8515, BASF, germany.
Polyethyleneimine B: weight average molecular weight 25000, trade name Lupasol HF, BASF, germany.
Polyethyleneimine C: weight average molecular weight 750000, trade name Lupasol P, BASF, germany.
Polyethyleneimine D: weight average molecular weight 1000000, trade name Lupasol PN 50, BASF, germany.
Polyethyleneimine E: weight average molecular weight 800, trade name Lupasol FG, BASF, germany.
Polyethyleneimine F: the weight average molecular weight is 2000000, trade name Lupasol SK, BASF, germany.
Preparation of polyamide compositions of examples and comparative examples: the other components except the glass fiber are evenly mixed, fed into a double-screw extruder through a main feeding port for extrusion granulation, the length-diameter ratio of a screw is 40:1, the temperature of a screw barrel is segmented to 260/260/250/240/230/230/230/240/260 ℃, the rotating speed of the screw is 300rpm, and if glass fiber or talcum powder is fed in a side mode, the polyamide composition is obtained.
The testing method comprises the following steps:
(1) Dry encapsulation test: two soft gel materials are selected for evaluation, including TPE and TPV materials which are common in the market and can be used for nylon cladding. The evaluation was performed using a soft rubber-coated hard rubber grinder, first, a polyamide rectangular plate 200mm long, 50mm wide and 2.5mm thick was injection-molded using the polyamide compositions prepared in the examples and comparative examples, and the rectangular plate was left to cool for 24 hours; the grinding tool fixed die surface is replaced by a soft rubber injection molding fixed die, the injection molded rectangular plate is embedded into the movable die surface, the soft rubber part is further injection molded, 10 groups of samples are respectively injection molded by TPE and TPV soft rubber, and the product of the soft rubber polyamide rectangular plate hard rubber is placed and cooled for 24 hours and then used for subsequent cohesive force testing.
The products of the soft adhesive and the hard adhesive are tested by using a specially modified adhesive force testing machine, and a testing method for the tearing resistance (cutting tearing) of the plastic film and the thin plate by referring to ASTM D1004-07 is built by equipment; in the test process, fixing the hard rubber part, clamping the soft rubber part, and carrying out a tension tearing test at the speed of 50mm/min until the soft rubber is broken or the soft rubber and the hard rubber are completely separated, and ending the test; and (3) observing the separation condition of the soft rubber and the hard rubber, wherein the judgment standard is as follows:
Comparison of encapsulation effect grades:
Stage 1: until the soft rubber is torn or broken, the soft rubber and the hard rubber are not obviously separated; or the soft rubber is completely torn, but the surface of the hard rubber is fully paved with the residual soft rubber and is not separated; exhibits excellent adhesion;
2 stages: until the soft rubber is torn or broken, the soft rubber and the hard rubber are only slightly separated, and the separation area is less than 5% of the total rubber coating area; exhibit good adhesion;
3 stages: until the soft rubber is torn or broken, the soft rubber and the hard rubber are obviously separated, and the separation area accounts for 5-20% of the encapsulation area; exhibit acceptable adhesion;
4 stages: until the soft rubber is torn or broken, the soft rubber and the hard rubber are obviously separated, and the separation area accounts for 20-80% of the encapsulation area; exhibit poor adhesion;
5 stages: until the soft rubber is torn or broken, the soft rubber and the hard rubber are obviously separated, and the separation area occupies more than 80 percent of the encapsulation area or is completely peeled; exhibiting poor adhesion.
(2) Encapsulation after aging test: the above test procedure was repeated after aging at 85℃and 85% humidity for 48 hours.
Table 1: examples 1-7 Polyamide compositions component content (parts by weight) and test results
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | |
| PA66-A | 100 | 100 | |||||
| PA66-B | 100 | ||||||
| PA66-C | 100 | ||||||
| PA66-D | 100 | ||||||
| PA6-A | 100 | ||||||
| PA610 | 100 | ||||||
| Glass fiber | 70 | 70 | 70 | 70 | 70 | 70 | |
| Talc powder | 70 | ||||||
| Epoxy auxiliary A | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
| Polyethyleneimine A | 0.7 | 0.7 | 0.7 | 0.7 | 0.7 | 0.7 | 0.7 |
| TPE (thermoplastic elastomer) coated polyamide hard rubber and grade | Level 1 | Level 1 | Level 1 | Level 1 | Level 1 | Level 1 | Level 1 |
| TPV (thermoplastic polyurethane) coated polyamide hard rubber, grade | Level 1 | Level 1 | Level 1 | Level 2 | Level 1 | Level 2 | Level 1 |
| TPE (thermoplastic elastomer) coated polyamide hard rubber after double 85 aging test | Level 2 | Level 1 | Level 1 | Level 2 | Level 2 | Level 2 | Level 2 |
| TPV (thermoplastic polyurethane) coated polyamide hard rubber after double 85 aging test | Level 2 | Level 1 | Level 2 | Level 2 | Level 2 | Level 2 | Level 2 |
As is evident from examples 1 to 6, the technical effect of the polyamide composition is better at the preferred terminal amino group content.
Table 2: examples 8-14 Polyamide compositions component contents (parts by weight) and test results
| Example 8 | Example 9 | Example 10 | Example 11 | Example 12 | Example 13 | Example 14 | |
| PA66-B | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Glass fiber | 70 | 70 | 70 | 70 | 70 | 70 | 70 |
| Epoxy auxiliary A | 0.03 | 0.07 | 0.3 | 1.5 | 4 | 6 | 7 |
| Polyethyleneimine A | 0.07 | 0.03 | 0.3 | 0.6 | 1 | 2 | 3 |
| TPE (thermoplastic elastomer) coated polyamide hard rubber and grade | Level 1 | Level 1 | Level 1 | Level 1 | Level 1 | Level 1 | Level 2 |
| TPV (thermoplastic polyurethane) coated polyamide hard rubber, grade | Level 2 | Level 2 | Level 1 | Level 1 | Level 1 | Level 1 | Level 1 |
| TPE (thermoplastic elastomer) coated polyamide hard rubber after double 85 aging test | Level 2 | Level 2 | Level 1 | Level 1 | Level 1 | Level 2 | Level 2 |
| TPV (thermoplastic polyurethane) coated polyamide hard rubber after double 85 aging test | Level 2 | Level 2 | Level 1 | Level 1 | Level 1 | Level 2 | Level 2 |
As is evident from examples 8 to 14, the preferred formulation has better technical results, in particular better aging resistance.
Table 3: examples 15-21 Polyamide compositions component contents (parts by weight) and test results
| Example 15 | Example 16 | Example 17 | Example 18 | Example 19 | Example 20 | Example 21 | Example 22 | Example 23 | |
| PA66-A | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Glass fiber | 70 | 70 | 70 | 70 | 70 | 70 | 70 | 70 | 10 |
| Epoxy auxiliary A | 1 | 1 | 1 | 1 | 1 | 1 | |||
| Epoxy auxiliary B | 1 | ||||||||
| Epoxy auxiliary C | 1 | ||||||||
| Epoxy auxiliary D | 1 | ||||||||
| Polyethyleneimine A | 0.7 | 0.7 | 0.7 | 0.7 | |||||
| Polyethylene imine B | 0.7 | ||||||||
| Polyethyleneimine C | 0.7 | ||||||||
| Polyethyleneimine D | 0.7 | ||||||||
| Polyethyleneimine E | 0.7 | ||||||||
| Polyethyleneimine F | 0.7 | ||||||||
| TPE (thermoplastic elastomer) coated polyamide hard rubber and grade | Level 1 | Level 2 | Level 2 | Level 1 | Level 1 | Level 1 | Level 1 | Level 1 | Level 1 |
| TPV (thermoplastic polyurethane) coated polyamide hard rubber, grade | Level 2 | Level 2 | Level 1 | Level 1 | Level 1 | Level 1 | Level 1 | Level 1 | Level 1 |
| TPE (thermoplastic elastomer) coated polyamide hard rubber after double 85 aging test | Level 2 | Level 2 | Level 2 | Level 1 | Level 1 | Level 2 | Level 2 | Level 2 | Level 1 |
| TPV (thermoplastic polyurethane) coated polyamide hard rubber after double 85 aging test | 3 Grade | Level 2 | Level 2 | Level 1 | Level 1 | Level 2 | 3 Grade | 3 Grade | Level 2 |
As is clear from examples 1/15-17, the epoxy auxiliary is preferably an epoxy resin.
As is clear from examples 1/18 to 22, polyethyleneimine is preferable to have a better aging resistance in the weight average molecular weight range.
Table 4: examples 22-24 Polyamide compositions each component content (parts by weight) and test results
| Example 22 | Example 23 | Example 24 | |
| PA1010 | 100 | ||
| PAMXD6 | 100 | ||
| PA66/6T | 100 | ||
| Glass fiber | 70 | 70 | 70 |
| Epoxy auxiliary A | 1 | 1 | 1 |
| Polyethyleneimine A | 0.7 | 0.7 | 0.7 |
| TPE (thermoplastic elastomer) coated polyamide hard rubber and grade | Level 1 | Level 2 | Level 2 |
| TPV (thermoplastic polyurethane) coated polyamide hard rubber, grade | Level 2 | Level 2 | Level 2 |
| TPE (thermoplastic elastomer) coated polyamide hard rubber after double 85 aging test | Level 2 | Level 2 | Level 2 |
| TPV (thermoplastic polyurethane) coated polyamide hard rubber after double 85 aging test | Level 2 | Level 2 | Level 2 |
As is clear from examples 1/5/6/22-24, aliphatic polyamides are preferred for better encapsulation, and PA66 and PA6 are further preferred.
Table 5: comparative example Polyamide composition content (parts by weight) and test results
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | |
| PA66-A | 100 | 100 | 100 | 100 | 100 | 100 |
| Glass fiber | 70 | 70 | 70 | 70 | 70 | 70 |
| Epoxy auxiliary A | 1 | 1 | 0.01 | 8 | 8 | |
| Polyethyleneimine A | 0.01 | 4 | 0.7 | 0.7 | 4 | |
| TPE (thermoplastic elastomer) coated polyamide hard rubber and grade | Level 2 | Level 1 | Level 2 | 3 Grade | Level 2 | 3 Grade |
| TPV (thermoplastic polyurethane) coated polyamide hard rubber, grade | Level 2 | Level 2 | 3 Grade | Level 2 | Level 2 | Grade 4 |
| TPE (thermoplastic elastomer) coated polyamide hard rubber after double 85 aging test | 3 Grade | Level 2 | Grade 4 | Grade 4 | 3 Grade | Grade 4 |
| TPV (thermoplastic polyurethane) coated polyamide hard rubber after double 85 aging test | Grade 4 | Grade 4 | Grade 4 | 3 Grade | Grade 4 | Grade 5 |
As is clear from comparative examples 1/2, when the amount of polyethyleneimine added is too low or too high, both the rubber coating property and the dual 85 aging resistance are poor.
As is clear from comparative examples 3/4, the addition amount of the epoxy auxiliary agent is too low or too high, and both the adhesive coating property and the dual 85 aging resistance are poor.
As is clear from comparative example 5, when the amounts of the polyethyleneimine and the epoxy auxiliary agent added are too high, both the rubber coating property and the aging resistance are poor.
Continuing with table 5:
| Comparative example 7 | Comparative example 8 | |
| PA66-E | 100 | |
| PA6-B | 100 | |
| Glass fiber | 70 | 70 |
| Epoxy auxiliary A | 1 | 1 |
| Polyethyleneimine A | 0.7 | 0.7 |
| TPE (thermoplastic elastomer) coated polyamide hard rubber and grade | 3 Grade | 3 Grade |
| TPV (thermoplastic polyurethane) coated polyamide hard rubber, grade | 3 Grade | 3 Grade |
| TPE (thermoplastic elastomer) coated polyamide hard rubber after double 85 aging test | 3 Grade | 3 Grade |
| TPV (thermoplastic polyurethane) coated polyamide hard rubber after double 85 aging test | 3 Grade | Grade 4 |
As is clear from comparative examples 7/8, the encapsulation property is poor when the terminal amino group of the polyamide resin is less than 45 mmol/kg.
Claims (16)
1. A polyamide composition characterized by comprising the following components in parts by weight: 100 parts of polyamide with an amino end value of 47-190mmol/kg, and epoxy auxiliary agent with the total weight of 0.0003-0.07 times of the total weight of the polyamide and polyethyleneimine with the total weight of 0.0003-0.03 times of the total weight of the polyamide, wherein the total addition amount of the epoxy auxiliary agent and the polyethyleneimine is not less than 0.1 part; the epoxy auxiliary agent is at least one selected from epoxy resin or copolymer containing glycidyl methacrylate monomer.
2. The polyamide composition according to claim 1, wherein the polyamide has an amino end value of 85 to 120mmol/kg.
3. The polyamide composition according to claim 1, wherein the copolymer containing a glycidyl methacrylate monomer is at least one selected from the group consisting of ethylene-butyl acrylate-glycidyl methacrylate copolymer, ethylene-methyl acrylate-glycidyl methacrylate copolymer, ethylene-butyl acrylate-glycidyl methacrylate grafted polyolefin elastomer.
4. The polyamide composition of claim 1 wherein the epoxy adjuvant is selected from the group consisting of epoxy resins.
5. The polyamide composition of claim 1, wherein the weight average molecular weight of the polyethyleneimine is in the range of 800 to 2000000.
6. The polyamide composition of claim 5 wherein the weight average molecular weight of the polyethyleneimine is in the range of 1300 to 1000000.
7. The polyamide composition of claim 6 wherein the weight average molecular weight of the polyethyleneimine is in the range of 25000 to 750000.
8. The polyamide composition according to claim 1, wherein the epoxy auxiliary is present in an amount of 0.003 to 0.04 times the total weight of the polyamide and the polyethyleneimine is present in an amount of 0.003 to 0.01 times the total weight of the polyamide.
9. The polyamide composition according to claim 1, wherein the polyamide is at least one selected from the group consisting of aliphatic polyamides obtained by polycondensation of at least one aliphatic dicarboxylic acid and at least one aliphatic diamine and/or polyamide obtained by polycondensation of at least one amino acid or at least one lactam with itself, and semi-aromatic polyamides obtained by polycondensation of at least one aromatic dicarboxylic acid and at least one aliphatic diamine.
10. The polyamide composition according to claim 1, wherein the polyamide is at least one selected from PA MXD6, PA MXD 10.
11. The polyamide composition of claim 9, wherein the aliphatic polyamide is selected from at least one of PA46, PA56, PA510, PA66, PA610, PA612, PA1010, PA1012, PA1212, PA6, PA7, PA11, PA 12; the semi-aromatic polyamide is selected from at least one of PA10T, PA T1010, PA10T66, PA66/6T, PA6T, PA9T, PA T/66.
12. Polyamide composition according to claim 9, characterized in that the polyamide is chosen from aliphatic polyamides.
13. The polyamide composition of claim 1, further comprising 0 to 200 parts by weight of a filler; the filler is at least one selected from fibrous filler and granular filler; the fibrous filler is at least one selected from glass fiber and carbon fiber; the granular filler is at least one selected from alumina, carbon black, aluminosilicate clay, montmorillonite, zirconium phosphate, kaolin, calcium carbonate, diatomite, graphite, mica, silica, titanium dioxide, zeolite, talcum powder, wollastonite, glass beads and glass powder.
14. The polyamide composition according to claim 1, further comprising 0 to 3 parts by weight of an auxiliary agent selected from at least one of an antioxidant, a lubricant, a weather-resistant agent, and a nucleating agent.
15. A process for the preparation of a polyamide composition as claimed in claim 14, comprising the steps of: and (3) uniformly mixing all components except the filler, feeding the components into a double-screw extruder through a main feeding port for extrusion granulation, wherein the length-diameter ratio of a screw is 36-52:1, the temperature range of a screw barrel is 180-300 ℃, the rotating speed is 200-700rpm, and feeding the components at the filler side to obtain the polyamide composition.
16. Use of a polyamide composition according to any one of claims 1 to 14 for the preparation of a soft gel coated article.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103958609A (en) * | 2011-11-25 | 2014-07-30 | 巴斯夫欧洲公司 | Blow-mouldable polyamide compound |
| CN104592749A (en) * | 2015-02-03 | 2015-05-06 | 上海日之升新技术发展有限公司 | Low-moisture-absorption long-term heat-resistant aging-resistant polyamide composition and preparation method thereof |
| CN108770359A (en) * | 2016-03-03 | 2018-11-06 | 大赛璐塑料株式会社 | Amilan polyamide resin composition |
| CN112194894A (en) * | 2020-09-29 | 2021-01-08 | 金发科技股份有限公司 | Halogen-free flame-retardant polyamide composite material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP3670576B8 (en) * | 2018-12-19 | 2020-12-09 | Ems-Chemie Ag | Polyamide moulding material for glass compositions |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103958609A (en) * | 2011-11-25 | 2014-07-30 | 巴斯夫欧洲公司 | Blow-mouldable polyamide compound |
| CN104592749A (en) * | 2015-02-03 | 2015-05-06 | 上海日之升新技术发展有限公司 | Low-moisture-absorption long-term heat-resistant aging-resistant polyamide composition and preparation method thereof |
| CN108770359A (en) * | 2016-03-03 | 2018-11-06 | 大赛璐塑料株式会社 | Amilan polyamide resin composition |
| CN112194894A (en) * | 2020-09-29 | 2021-01-08 | 金发科技股份有限公司 | Halogen-free flame-retardant polyamide composite material and preparation method thereof |
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