WO2023272459A1 - 一种聚酰胺及其制备方法 - Google Patents
一种聚酰胺及其制备方法 Download PDFInfo
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- WO2023272459A1 WO2023272459A1 PCT/CN2021/102893 CN2021102893W WO2023272459A1 WO 2023272459 A1 WO2023272459 A1 WO 2023272459A1 CN 2021102893 W CN2021102893 W CN 2021102893W WO 2023272459 A1 WO2023272459 A1 WO 2023272459A1
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- polyamide
- component
- dicarboxylic acid
- reaction
- carbon atoms
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 70
- 229920002647 polyamide Polymers 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 45
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 15
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 6
- -1 aliphatic diamine Chemical class 0.000 claims abstract description 4
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 33
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 26
- 238000006297 dehydration reaction Methods 0.000 claims description 17
- 239000008188 pellet Substances 0.000 claims description 17
- 239000000155 melt Substances 0.000 claims description 16
- 239000000654 additive Substances 0.000 claims description 7
- 150000004985 diamines Chemical class 0.000 claims description 7
- 239000004033 plastic Substances 0.000 claims description 7
- 229920003023 plastic Polymers 0.000 claims description 7
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 6
- 239000003365 glass fiber Substances 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 claims description 4
- 238000005259 measurement Methods 0.000 claims description 3
- 238000011089 mechanical engineering Methods 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 claims description 2
- 239000004609 Impact Modifier Substances 0.000 claims description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 2
- 239000002318 adhesion promoter Substances 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 239000002216 antistatic agent Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000002482 conductive additive Substances 0.000 claims description 2
- 239000002826 coolant Substances 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000000314 lubricant Substances 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 claims description 2
- 239000012763 reinforcing filler Substances 0.000 claims description 2
- 239000012779 reinforcing material Substances 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 238000005266 casting Methods 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 18
- 238000002844 melting Methods 0.000 description 18
- 230000008018 melting Effects 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 238000004512 die casting Methods 0.000 description 15
- 229910001873 dinitrogen Inorganic materials 0.000 description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 239000001361 adipic acid Substances 0.000 description 9
- 235000011037 adipic acid Nutrition 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000012545 processing Methods 0.000 description 9
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 6
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000000071 blow moulding Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000015784 hyperosmotic salinity response Effects 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 229920006012 semi-aromatic polyamide Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- 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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Definitions
- the present application relates to polyamide products, in particular to a polyamide and its preparation method and composition.
- the invention also relates to compositions comprising at least one of said polyamides and to articles produced from said compositions.
- the invention also relates to the use of the article in the fields of motor vehicles, electronics, sports equipment, fluid pipelines, mechanical engineering, food utensils, leisure, toys, measurement and control technology.
- PA Polyamide
- PA66 and PA6 are the varieties with the largest output in the PA family. They have suitable production costs and can meet the needs of common usage scenarios. However, it also has disadvantages such as poor salt tolerance, high water absorption and poor hydrolysis resistance. Later, researchers made up for the shortage of PA66 and PA6 by developing long carbon chain PA.
- the ratio of the number of methylene groups to the number of amide bonds in the main chain of the long carbon chain PA molecule is not less than 7.
- Long carbon chain PA not only has most of the common properties of general PA, such as lubricity, wear resistance and compression resistance, and easy processing, but also has good toughness and softness, low water absorption, good dimensional stability, salt resistance and hydrolysis resistance. , low density and other characteristics.
- the melting point of long carbon chain PA has decreased to varying degrees.
- the melting point of PA612 is 218°C, which is significantly lower than the melting point of PA66 at 262°C, so that the temperature resistance of long carbon chain nylon is significantly lower than that of PA66.
- Semi-aromatic polyamide also known as PPA
- PPA Semi-aromatic polyamide
- PA66 and PA6 due to the presence of aromatic rings in the molecular chain, has significantly higher salt and chemical resistance than PA66 and PA6.
- PA66 and PA6 due to its high melting point of about 300°C or higher, it greatly increases its manufacturing difficulty.
- high processing temperature puts forward higher requirements for processing equipment, which increases processing cost and energy consumption. Extrusion and blow molding applications.
- the application provides a polyamide and a preparation method thereof, the polyamide has an aliphatic diamine structure of 8-14 carbon atoms, has better chemical resistance than PA66, and is relatively Conventional long-chain nylons with the same carbon atoms in the main chain, such as PA610, PA612, etc., have higher melting points and heat resistance properties, and have lower processing temperatures than PPA, reducing equipment requirements and energy consumption, and can be used for injection molding , extrusion and blow molding products.
- the present application provides a polyamide PAXY/XZ, which is polymerized from the following components:
- X is an aliphatic diamine containing 8 to 14 carbon atoms without side chains
- Y is an aliphatic diacid with no side chains containing 4 to 10 carbon atoms, and the total number of carbon atoms in X is at least 2 more than the total number of carbon atoms in Y;
- Z is aromatic dicarboxylic acid or/and alicyclic dicarboxylic acid
- the mole fraction of XY in the polyamide PAXY/XZ is 40-100%, the mole fraction of XZ is 0-60%, and the sum of the mole contents of XY and XZ is 100%.
- the preferred molar content of XZ is 0 or 20-50%.
- the sum of the molar amounts of all diamines is substantially equal to the sum of the molar amounts of all dicarboxylic acids.
- substantially equal to means a maximum molar excess of dicarboxylic acid or diamine of 4%, preferably a maximum molar excess of dicarboxylic acid or diamine of 2%, which means a molar ratio of dicarboxylic acid to diamine of 1.04 :1 to 1:1.04, the preferred molar ratio of dicarboxylic acid to diamine is 1.02:1 to 1:1.02.
- the aromatic dicarboxylic acid in the present invention is selected from one or more of terephthalic acid, 4,4'-biphenyldicarboxylic acid, and 2,6-naphthalene dicarboxylic acid, preferably terephthalic acid;
- the aliphatic cyclic dicarboxylic acid in the present invention is selected from 1,4-cyclohexanedicarboxylic acid.
- the present application provides a kind of preparation method of polyamide on the other hand, comprises the steps:
- a suitable catalyst added to accelerate the polymerization reaction is a phosphorus-containing acid, such as H 3 PO 2 , H 3 PO 3 , H 3 PO 4 and their salts or organic derivatives;
- the present invention also provides a polyamide composition comprising:
- component B in the composition is glass fiber and/or carbon fiber at least to a certain extent, and these fibers can be short fibers of 2-50 mm, or continuous long fibers, and the glass fiber and/or carbon fiber have round shaped or non-circular cross-section.
- component C of the composition comprises additives and/or other polymers selected from the group consisting of impact modifiers, adhesion promoters, compatibilizers, crystallization promoters or retarders, flow aids, lubricating Agents, release agents, pigments, plasticizers, stabilizers, processing aids, flame retardants, antistatic agents, conductive additives, polymerization process additives.
- additives and/or other polymers selected from the group consisting of impact modifiers, adhesion promoters, compatibilizers, crystallization promoters or retarders, flow aids, lubricating Agents, release agents, pigments, plasticizers, stabilizers, processing aids, flame retardants, antistatic agents, conductive additives, polymerization process additives.
- the present invention also provides a plastic part comprising the aforementioned polyamide composition, preferably the plastic part consists of a molding compound.
- Molded, extruded and blow molded parts can be produced by standard processing techniques for polyamides.
- moldings can be carried out by conventional injection molding machines with standard 3-stage screws at barrel temperatures 10-60°C above the melting point.
- the mold temperature is set at 40-130°C, preferably 70-100°C.
- the plastic parts of the present invention can be used in automobiles, especially parts in direct contact with coolant, and/or fluid pipelines; electronic and electrical devices, especially portable electronic devices such as mobile phones, smart watches, smart bracelets, laptops , game consoles, VR glasses, tablet computers, cameras, etc.; sports equipment; non-automotive fluid pipelines; mechanical engineering; food utensils; leisure; toys; measurement and control technology.
- the polyamide PAXY/XZ and its composition obtained in the present invention have higher melting point, heat distortion temperature and temperature resistance. Compared with PA66, it has better chemical resistance.
- a kind of polyamide, its preparation method comprises the steps:
- a kind of polyamide, its preparation method comprises the steps:
- Component 1 with a molar content of 50% a mixture of decanediamine and adipic acid with a molar ratio of 1:1;
- Component 2 with a molar content of 50% a mixture of decanediamine and terephthalic acid in a molar ratio of 1:1;
- Component 1 with a molar content of 80% a mixture of decanediamine and adipic acid in a molar ratio of 1:1;
- Component 2 with a molar content of 20% a mixture of decanediamine and terephthalic acid in a molar ratio of 1:1;
- Component 1 with a molar content of 70% a mixture of decanediamine and adipic acid with a molar ratio of 1:1;
- Component 2 with a molar content of 30% a mixture of decanediamine and 1,4-cyclohexanedicarboxylic acid in a molar ratio of 1:1;
- Component 1 with a molar content of 80% a mixture of decanediamine and adipic acid in a molar ratio of 1:1;
- Component 2 with a molar content of 20% a mixture of decanediamine and 2,6-naphthalene dicarboxylic acid in a molar ratio of 1:1;
- Component 1 with a molar content of 80% a mixture of decanediamine and adipic acid in a molar ratio of 1:1;
- Component 2 with a molar content of 20% a mixture of decanediamine, terephthalic acid and 1,4-cyclohexanedicarboxylic acid in a molar ratio of 1:0.5:0.5;
- Component 1 with a molar content of 80% a mixture of dodecylamine and adipic acid with a molar ratio of 1:1;
- Component 2 with a molar content of 20% a mixture of dodecylamine and terephthalic acid in a molar ratio of 1:1;
- Component 1 with a molar content of 80% a mixture of dodecylamine and adipic acid with a molar ratio of 1:1;
- Component 2 with a molar content of 20% a mixture of dodecylamine, terephthalic acid and 1,4-cyclohexanedicarboxylic acid in a molar ratio of 1:0.5:0.5;
- a kind of polyamide, its preparation method comprises the steps:
- a kind of polyamide, its preparation method comprises the steps:
- Component 1 with a molar content of 80% a mixture of hexamethylenediamine and sebacic acid at a molar ratio of 1:1;
- Component 2 with a molar content of 20% a mixture of hexamethylenediamine and terephthalic acid at a molar ratio of 1:1;
- a kind of polyamide, its preparation method comprises the steps:
- a kind of polyamide, its preparation method comprises the steps:
- the melting point is tested according to the ISO 11357-3-2011 Plastics - Differential Scanning Calorimetry (DSC) method, and the melting peak is recorded.
- the heat resistance is tested according to the ISO 75-2 test method of heat distortion temperature under load, and the heat distortion temperature of 33% glass fiber reinforced is recorded.
- the tensile strength is tested on the ISO/CD3167 A1 type 170x20/10x4mm sample bar at 23°C according to ISO527, and the flexural strength and flexural modulus are tested on the same sample bar according to the ISO178 standard.
- the mixing of polyamide and glass fiber can be carried out by standard processing technology for polyamide, such as adopting a twin-screw extruder with an aspect ratio of 48 in the present invention, the diameter of the screw is 30mm, and the temperature of the extruder barrel is set at The melting point is 20°C higher than that of polyamide. After blending, the mixture strips are cooled in a water tank and then pelletized.
- standard processing technology for polyamide such as adopting a twin-screw extruder with an aspect ratio of 48 in the present invention, the diameter of the screw is 30mm, and the temperature of the extruder barrel is set at The melting point is 20°C higher than that of polyamide.
- the notched impact strength is tested according to ISO179/keU on ISO/CD3167 B1 type 80x10x4mm spline at 23°C
- Example 1 PA106 has the same number of carbon atoms relative to the main chain. Comparative Example 1 PA610 has a melting point 19°C higher and a heat distortion temperature 20°C higher. After introducing terephthalic acid, 1,4-cyclohexanedicarboxylic acid and 2,6-naphthalene dicarboxylic acid in Examples 3 to 7, the melting point of polyamide can be further improved, and the melting point is significantly lower than that of traditional PPA by about 300°C Melting point, reducing requirements on processing equipment and helping to reduce energy consumption.
- PA106/10T (80% mole 106:20% mole 10T; here T represents terephthalic acid) in embodiment 4
- PA610/6T 80% mole 610 : 20% mol 6T; where T represents terephthalic acid
- the melting point is 46°C higher
- the heat distortion temperature is 42°C higher.
- PA126 has the same number of carbon atoms relative to the main chain.
- PA612 has a melting point 10°C higher and a heat distortion temperature 13°C higher.
- the melting point of polyamide can be further increased after introducing terephthalic acid and 1,4-in Examples 8 to 9.
Abstract
一种聚酰胺及其制备方法，其中聚酰胺PA XY/XZ由下述组分聚合而成：X为含有8到14个碳原子的不含侧链的脂肪族二胺；Y为含有4到10个碳原子的不含侧链的脂肪族二酸，且X中碳原子总数比Y中碳原子总数至少多于2；Z为芳族二羧酸或/和脂肪环状二羧酸或/和它们的混合物；聚酰胺PA XY/XZ中XY摩尔分数为40-100%，XZ摩尔分数为0-60%，XY和XZ摩尔含量总和为100%。此外还涉及包含所述聚酰胺的组合物和制品。
Description
本申请涉及聚酰胺制品，尤其涉及一种聚酰胺及其制备方法和组合物。本发明还涉及包含至少一种所述聚酰胺的组合物和由所述组合物制成的制件。本发明还涉及该制件在机动车、电子电气、运动器材、流体管路、机械工程、食品用具、休闲、玩具、测量和控制技术领域的用途。
聚酰胺(以下简称为PA)，具有优异的力学、耐高温、耐磨、耐油和加工性能，已成为人类社会生活中不可或缺的生产资料，被广泛应用于电子电气、汽车、建筑、办公设备、机械、航空航天等行业，在国民经济领域发挥着十分重要的作用。
PA66和PA6是PA家族中产量最大的品种，具有合适的生产成本，能满足常见使用场景的需求。然而，其也具有耐盐差、吸水性高和耐水解性能差等缺点。后来科研人员通过开发长碳链PA来弥补PA66和PA6的不足。长碳链PA分子主链中的亚甲基数目和酰胺键数目之比不小于7。长碳链PA除具备一般PA的大多通用性能如润滑性、耐磨抗压和易加工性等，还具备韧性和柔软性好、吸水率低、尺寸稳定性好、耐盐和耐水解性能好、密度低等特点。相对于PA66，长碳链PA的熔点有不同程度的下降，比如PA612的熔点为218℃，明显低于PA66 262℃熔点，从而使得长碳链尼龙耐温性能相对于PA66明显下降。
半芳香族聚酰胺(又称PPA)，由于分子链中芳环的存在，其耐盐和耐化性能明显高于PA66和PA6。然而由于其高达300℃左右或者更高的熔点，大大增加了其制造难度，另外高加工温度对加工设备提出了更高要求，提高了加工成本和加工能耗，高加工温度也限制了其在挤出制件和吹塑制件的应用。
发明内容
为了克服现有技术的不足，本申请提供了一种聚酰胺及其制备方法，该聚酰胺具有8-14个碳原子的脂肪族二胺结构，相对于PA66具有更好的耐化学性能，较主链具有相同碳原子的常规长链尼龙比如PA610、PA612等分别具有更高的熔点和耐热性能，相对于PPA具有更低的加工温度，减少对设备的要求以及能耗，可以用于注塑、挤出和吹塑制品。
为了实现上述目的，本申请一方面提供了一种聚酰胺PAXY/XZ，由下述组分聚合而成：
X为含有8到14个碳原子的不含侧链的脂肪族二胺；
Y为含有4到10个碳原子的不含侧链的脂肪族二酸，且X中碳原子总数比Y中碳原子总数至少多于2；
Z为芳族二羧酸或/和脂肪环状二羧酸；
聚酰胺PAXY/XZ中XY摩尔分数为40-100％，XZ摩尔分数为0-60％，XY和XZ摩尔含量总和为100％。优选的XZ的摩尔含量为0或者20～50％。在形成聚酰胺的二羧酸和二胺量值中，所有二胺的摩尔量的总和基本等于所有二羧酸的摩尔量的总和。“基本上等于”指二羧酸或二胺的最大摩尔过量为4％，优选的二羧酸或二胺的最大摩尔过量为2％，这意味着二羧酸与二胺的摩尔比例为1.04:1至1:1.04，优选的二羧酸与二胺的摩尔比例为1.02:1至1:1.02。
本发明所述芳族二羧酸选自对苯二甲酸、4,4'-联苯二羧酸、2,6-萘二羧酸中一种或多种，优选为对苯二甲酸；
本发明所述脂肪环状二羧酸选自1，4-环己烷二羧酸。
本申请另一方面提供了一种聚酰胺的制备方法，包括如下步骤：
1)将组分X、组分Y和组分Z加入去离子水后进行预成盐后输入聚合釜，或者直接输入聚合釜中，加入任何添加剂后在所述聚合釜中加热搅拌进行脱水反应，比如加入用于加速聚合反应的合适的催化剂是含磷的酸，例如H
3PO
2、H
3PO
3、H
3PO
4及其盐或者有机衍生物；
2)进行反应后，注入氮气排出反应生成的水分，然后再加压排出聚酰胺熔体，熔体通过模头铸带成型，经冷却切粒而得。
在聚合反应中通过加热搅拌、并进行脱水反应可使得短时间内高效率地将水排出反应体系，以提高反应速率，促进酰胺键的生成以形成所需的分子量。相对粘度和由此的分子量可以以已知的方式来调节。
本发明还提供了一种聚酰胺组合物，其包含：
A.30-100％重量通过根据权利要求1-4得到的至少一种聚酰胺PAXY/XZ；
B.0-70％重量的增强材料和/或填料；
C.0-50％重量添加剂和/或其它聚合物；
其中组分A至C总共100％。
优选地，所述组合物中组分B至少在一定程度上是玻璃纤维和/或碳纤维，这些纤维可以选择2-50mm短纤维，或者连续长纤维，并且所述玻璃纤维和/或碳纤维具有圆形或者非圆形横截面。
优选地，所述组合物中组分C包括选自以下的添加剂和/或其它聚合物：冲击改性 剂、粘合促进剂、增容剂、结晶促进或者阻滞剂、流动助剂、润滑剂、脱模剂、颜料、增塑剂、稳定剂、加工助剂、阻燃剂、抗静电剂、导电添加剂、聚合工艺添加剂。
本发明还提供一种塑料制件，其包含前述的聚酰胺组合物，优选的所述塑料制件由模塑料构成。模制件、挤出制件和吹塑制件可以通过用于聚酰胺的标准加工技术进行生产。比如模制件可以通过具有标准3段螺杆的常规注塑机中，在高于熔点10-60℃的机筒温度下进行的。模具温度设定为40-130℃，优选70-100℃。
本发明所述的塑料制件可以用在在汽车特别是与冷却液直接接触的部件、和/或流体管路；电子电气特别是便携式电子装置如移动电话、智能手表、智能手环、便携式电脑、游戏机、VR眼镜、平板电脑、照相机等；运动器材；非汽车用途流体管路；机械工程；食品用具；休闲；玩具；测量和控制技术领域。
本发明得到的聚酰胺PAXY/XZ及其组合物，相对于传统长链尼龙比如PA612，具有更高的熔点、热变形温度和耐温性能。相对于PA66具有更好的耐化学性能。
下面通过具体实施方式来进一步说明本申请的技术方案，但不构成对本申请的任何限制。
以下对于本申请的聚酰胺及其制备方法利用实施例进行详细的说明，实施例中的原料皆可通过市售获得。
实施例1
一种聚酰胺，其制备方法包括如下步骤：
1)在50L带有搅拌器的自动控制聚合釜中加入10kg去离子水，然后加入摩尔比为1:1的癸二胺和己二酸的混合物25kg，在聚合釜的压力为20bar、温度为280℃下进行脱水反应；
2)进行反应后，注入氮气排出反应生成的水分，然后再加压排出聚酰胺熔体，熔体通过模头铸带成型，经冷却切粒而得。
实施例2
一种聚酰胺，其制备方法包括如下步骤：
1)在50L带有搅拌器的自动控制聚合釜中加入10kg去离子水，然后加入摩尔比为1:1的十二胺和己二酸的混合物25kg，在聚合釜的压力为20bar、温度为280℃下进行脱水反应；
2)进行反应后，注入氮气排出反应生成的水分，然后再加压排出聚酰胺熔体，熔体通过模头铸带成型，经冷却切粒而得。
实施例3
一种聚酰胺，由下述组分聚合而成：
摩尔含量为50％的组分一：摩尔比为1:1的癸二胺和己二酸的混合物；
摩尔含量为50％的组分二：摩尔比为1:1的癸二胺和对苯二甲酸的混合物；
其制备方法包括如下步骤：
1)在50L带有搅拌器的自动控制聚合釜中加入10kg去离子水，然后加入25kg组分一和组分二的混合物，在聚合釜的压力为25bar、温度为290℃下进行脱水反应；
2)进行反应后，注入氮气排出反应生成的水分，然后再加压排出聚酰胺熔体，熔体通过模头铸带成型，经冷却切粒而得。
实施例4
一种聚酰胺，由下述组分聚合而成：
摩尔含量为80％的组分一：摩尔比为1:1的癸二胺和己二酸的混合物；
摩尔含量为20％的组分二：摩尔比为1:1的癸二胺和对苯二甲酸的混合物；
其制备方法包括如下步骤：
1)在50L带有搅拌器的自动控制聚合釜中加入10kg去离子水，然后加入25kg组分一和组分二的混合物，加入1g磷酸，在聚合釜的压力为25bar、温度为290℃下进行脱水反应；
2)进行反应后，注入氮气排出反应生成的水分，然后再加压排出聚酰胺熔体，熔体通过模头铸带成型，经冷却切粒而得。
实施例5
一种聚酰胺，由下述组分聚合而成：
摩尔含量为70％的组分一：摩尔比为1:1的癸二胺和己二酸的混合物；
摩尔含量为30％的组分二：摩尔比为1:1的癸二胺和1，4-环己烷二羧酸的混合物；
其制备方法包括如下步骤：
1)在50L带有搅拌器的自动控制聚合釜中加入10kg去离子水，然后加入25kg组分一和组分二的混合物，加入0.5g磷酸，在聚合釜的压力为25bar、温度为285℃下进行脱水反应；
2)进行反应后，注入氮气排出反应生成的水分，然后再加压排出聚酰胺熔体，熔体通过模头铸带成型，经冷却切粒而得。
实施例6
一种聚酰胺，由下述组分聚合而成：
摩尔含量为80％的组分一：摩尔比为1:1的癸二胺和己二酸的混合物；
摩尔含量为20％的组分二：摩尔比为1:1的癸二胺和2，6-萘二羧酸的混合物；
其制备方法包括如下步骤：
1)在50L带有搅拌器的自动控制聚合釜中加入10kg去离子水，然后加入25kg组分一和组分二的混合物，加入1g磷酸，在聚合釜的压力为25bar、温度为290℃下进行脱水反应；
2)进行反应后，注入氮气排出反应生成的水分，然后再加压排出聚酰胺熔体，熔体通过模头铸带成型，经冷却切粒而得。
实施例7
一种聚酰胺，由下述组分聚合而成：
摩尔含量为80％的组分一：摩尔比为1:1的癸二胺和己二酸的混合物；
摩尔含量为20％的组分二：摩尔比为1:0.5:0.5的癸二胺、对苯二甲酸和1，4-环己烷二羧酸的混合物；
其制备方法包括如下步骤：
1)在50L带有搅拌器的自动控制聚合釜中加入10kg去离子水，然后加入25kg组分一和组分二的混合物，加入1g磷酸，在聚合釜的压力为25bar、温度为290℃下进行脱水反应；
2)进行反应后，注入氮气排出反应生成的水分，然后再加压排出聚酰胺熔体，熔体通过模头铸带成型，经冷却切粒而得。
实施例8
一种聚酰胺，由下述组分聚合而成：
摩尔含量为80％的组分一：摩尔比为1:1的十二胺和己二酸的混合物；
摩尔含量为20％的组分二：摩尔比为1:1的十二胺和对苯二甲酸的混合物；
其制备方法包括如下步骤：
1)在50L带有搅拌器的自动控制聚合釜中加入10kg去离子水，然后加入25kg组分一和组分二的混合物，加入1g磷酸，在聚合釜的压力为23bar、温度为285℃下进行脱水反应；
2)进行反应后，注入氮气排出反应生成的水分，然后再加压排出聚酰胺熔体，熔体通过模头铸带成型，经冷却切粒而得。
实施例9
一种聚酰胺，由下述组分聚合而成：
摩尔含量为80％的组分一：摩尔比为1:1的十二胺和己二酸的混合物；
摩尔含量为20％的组分二：摩尔比为1:0.5:0.5的十二胺、对苯二甲酸和1，4-环己烷二羧酸的混合物；
其制备方法包括如下步骤：
1)在50L带有搅拌器的自动控制聚合釜中加入10kg去离子水，然后加入25kg组分一和组分二的混合物，加入1g磷酸，在聚合釜的压力为23bar、温度为285℃下进行脱水反应；
2)进行反应后，注入氮气排出反应生成的水分，然后再加压排出聚酰胺熔体，熔体通过模头铸带成型，经冷却切粒而得。
对比例1
一种聚酰胺，其制备方法包括如下步骤：
1)在50L带有搅拌器的自动控制聚合釜中加入10kg去离子水，然后加入摩尔比为1:1的己二胺和癸二酸的混合物25kg，在聚合釜的压力为20bar、温度为280℃下进行脱水反应；
2)进行反应后，注入氮气排出反应生成的水分，然后再加压排出聚酰胺熔体，熔体通过模头铸带成型，经冷却切粒而得。
对比例2
一种聚酰胺，其制备方法包括如下步骤：
1)在50L带有搅拌器的自动控制聚合釜中加入10kg去离子水，然后加入摩尔比为1:1的己二胺和十二酸的混合物25kg，在聚合釜的压力为20bar、温度为280℃下进行脱水反应；
2)进行反应后，注入氮气排出反应生成的水分，然后再加压排出聚酰胺熔体，熔体通过模头铸带成型，经冷却切粒而得。
对比例3
一种聚酰胺，由下述组分聚合而成：
摩尔含量为80％的组分一：摩尔比为1:1的己二胺和癸二酸的混合物；
摩尔含量为20％的组分二：摩尔比为1:1的己二胺和对苯二甲酸的混合物；
其制备方法包括如下步骤：
1)在50L带有搅拌器的自动控制聚合釜中加入10kg去离子水，然后加入25kg组分一和组 分二的混合物，在聚合釜的压力为25bar、温度为290℃下进行脱水反应；
2)进行反应后，注入氮气排出反应生成的水分，然后再加压排出聚酰胺熔体，熔体通过模头铸带成型，经冷却切粒而得。
对比例4
一种聚酰胺，其制备方法包括如下步骤：
1)在50L带有搅拌器的自动控制聚合釜中加入10kg去离子水，然后加入摩尔比为1:1的癸二胺和癸二酸的混合物25kg，在聚合釜的压力为20bar、温度为240℃下进行脱水反应；
2)进行反应后，注入氮气排出反应生成的水分，然后再加压排出聚酰胺熔体，熔体通过模头铸带成型，经冷却切粒而得。
对比例5
一种聚酰胺，其制备方法包括如下步骤：
1)在50L带有搅拌器的自动控制聚合釜中加入10kg去离子水，然后加入摩尔比为1:1的十二胺和十二酸的混合物25kg，在聚合釜的压力为18bar、温度为220℃下进行脱水反应；
2)进行反应后，注入氮气排出反应生成的水分，然后再加压排出聚酰胺熔体，熔体通过模头铸带成型，经冷却切粒而得。
1.测试方法
本申请的范围内使用以下测试方法：
相对粘度根据ISO 307(2007)，在20℃下测定相对粘度，称量0.5g聚合物粒料放入100ml的间甲酚中，按照该标准的第11章计算相对粘度RV
熔点根据ISO 11357-3-2011塑料-差示扫描量热法(DSC)方法进行测试，并记录熔融峰值。
耐热性根据ISO 75-2负荷下热变形温度测试方法进行测试，并记录33％玻纤增强后的热变形温度。
拉伸强度根据ISO527在23℃下对ISO/CD3167 A1型170x20/10x4mm样条进行测试，弯曲强度和弯曲模量采用ISO178标准对同种样条进行测试。
聚酰胺和玻纤混合可采用可以通过用于聚酰胺的标准加工技术实施，比如在本发明中采用长径比48的双螺杆挤出机，螺杆直径为30mm，挤出机筒温度设定为比聚酰胺熔点高20℃，共混后混合物料条经水槽冷却后切粒。
缺口冲击强度根据ISO179/keU对ISO/CD3167 B1型80x10x4mm样条在23℃测试
表1实施例1～4和对比例1～3的各性能测试结果
由表1可知，采用本申请的聚酰胺相对于传统长碳链聚酰胺具有更高的熔点和耐热性。实施例1中PA106相对于主链具有相同碳原子数的对比例1 PA610熔点高19℃，热变形温度高20℃。在实施例3至7中引入对苯二甲酸、1,4-环己烷二羧酸和2,6-萘二羧酸后可以进一步提升聚酰胺熔点，且熔点显著低于传统PPA 300℃左右熔点，降低对加工设备的要求以及有利于减少能耗。比如实施例4中PA106/10T(80％摩尔106：20％摩尔10T；此处T代表对苯二甲酸)，相对于主链具有相同碳原子数的对比例3 PA610/6T(80％摩尔610：20％摩尔6T；此处T代表对苯二甲酸)熔点高46℃，热变形温度高42℃。实施例2中PA126相对于主链具有相同碳原子数的对比例2 PA612熔点高10℃，热变形温度高13℃。在实施例8至9中引入对苯二甲酸和1，4-后可以进一步提升聚酰胺熔点。
应当指出，以上具体实施例仅用于说明本申请而不用于限制本申请的范围，在阅读了本申请之后，在本申请保护范围的宗旨内，本领域技术人员对本申请的各种等价形式的修改，如对各组分的含量的替换，脂肪族二元胺，芳香二元酸等物质具体组分的替换，制备参数的调整等应均落入本申请所附权利要求限定的范围。
Claims (10)
- 一种聚酰胺PAXY/XZ，其特征在于，所述聚酰胺由下述组分聚合而成：X为含有8到14个碳原子的不含侧链的脂肪族二胺；Y为含有4到10个碳原子的不含侧链的脂肪族二羧酸，且X中碳原子总数比Y中碳原子总数至少多2；Z为芳族二羧酸或/和脂肪环状二羧酸。
- 如权利要求1所述的聚酰胺PA XY/XZ，其特征在于，所述组分XY的摩尔含量为40～100％，所述组分XZ的摩尔含量为0～60％，所述组分XY和XZ摩尔含量总和为100％。
- 如权利要求1或2所述的聚酰胺PAXY/XZ,其特征在于所述组分中二羧酸的摩尔量与二胺的摩尔量比例为1.04：1至1：1.04。
- 如权利要求1所述的聚酰胺PAXY/XZ，其特征在于，所述芳族二羧酸选自对苯二甲酸、4,4'-联苯二羧酸、2,6-萘二羧酸中一种或多种；所述脂肪环状二羧酸为1,4-环己烷二羧酸。
- 如权利要求1～4任一项所述的聚酰胺PAXY/XZ的制备方法，其特征在于，包括如下步骤：1)将组分X、组分Y和组分Z输入聚合釜中，在所述聚合釜中加热搅拌进行脱水反应；2)反应结束后，排出聚酰胺熔体，熔体通过模头铸带成型，经冷却切粒而得。
- 一种聚酰胺组合物，其包含：A.30-100％重量的权利要求1-4所述的或权利要求5所述方法制备的至少一种聚酰胺PA XY/XZ；B.0-70％重量的增强材料和/或填料；C.0-50％重量添加剂和/或其它聚合物；其中组分A至C总共100％重量。
- 根据权利要求6所述一种聚酰胺组合物，其中组分B至少在一定程度上是玻璃纤维和/或碳纤维，这些纤维选自2-50mm短纤维或者连续长纤维，并且所述玻璃纤维和/或碳纤维具有圆形或者非圆形横截面。
- 根据权利要求7所述一种聚酰胺组合物，其中组分C包括选自以下的添加剂和/或其它聚合物：冲击改性剂、粘合促进剂、增容剂、结晶促进或者阻滞剂、流动助剂、润滑剂、脱模剂、颜料、增塑剂、稳定剂、加工助剂、阻燃剂、抗静电剂、导电添加剂、聚合工艺添加剂。
- 一种塑料制件，其包含权利要求6至8所述的聚酰胺组合物，优选的所述塑料制件由模 塑料构成。
- 权利要求9所述塑料制件在汽车特别是与冷却液直接接触的部件、和/或流体管路；电子电气特别是便携式电子装置如移动电话、智能手表、智能手环、便携式电脑、游戏机、VR眼镜、平板电脑、照相机等；运动器材；非汽车用途流体管路；机械工程；食品用具；休闲；玩具；测量和控制技术领域的用途。
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