CN115044196A - Preparation method of nylon alloy - Google Patents
Preparation method of nylon alloy Download PDFInfo
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- CN115044196A CN115044196A CN202110248831.0A CN202110248831A CN115044196A CN 115044196 A CN115044196 A CN 115044196A CN 202110248831 A CN202110248831 A CN 202110248831A CN 115044196 A CN115044196 A CN 115044196A
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- 229920001778 nylon Polymers 0.000 title claims abstract description 79
- 239000004677 Nylon Substances 0.000 title claims abstract description 76
- 239000000956 alloy Substances 0.000 title claims abstract description 75
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229920000642 polymer Polymers 0.000 claims abstract description 67
- 239000002994 raw material Substances 0.000 claims abstract description 59
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 45
- 238000001125 extrusion Methods 0.000 claims abstract description 39
- 150000004985 diamines Chemical class 0.000 claims abstract description 29
- 150000002148 esters Chemical class 0.000 claims abstract description 13
- 239000000155 melt Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 33
- 239000002253 acid Substances 0.000 claims description 31
- 239000000178 monomer Substances 0.000 claims description 15
- -1 polysiloxane Polymers 0.000 claims description 13
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 11
- 238000000354 decomposition reaction Methods 0.000 claims description 11
- 239000002612 dispersion medium Substances 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 10
- 239000004793 Polystyrene Substances 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 229920002492 poly(sulfone) Polymers 0.000 claims description 7
- 229920001296 polysiloxane Polymers 0.000 claims description 7
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 229920000098 polyolefin Polymers 0.000 claims description 6
- 229920002223 polystyrene Polymers 0.000 claims description 6
- 229920006295 polythiol Polymers 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 5
- 150000008065 acid anhydrides Chemical class 0.000 claims description 5
- 239000012467 final product Substances 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 abstract description 21
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 description 44
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 16
- 238000002844 melting Methods 0.000 description 14
- 230000008018 melting Effects 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000000203 mixture Substances 0.000 description 11
- 239000003963 antioxidant agent Substances 0.000 description 10
- 230000003078 antioxidant effect Effects 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 8
- 230000004580 weight loss Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000005469 granulation Methods 0.000 description 6
- 230000003179 granulation Effects 0.000 description 6
- 229920006139 poly(hexamethylene adipamide-co-hexamethylene terephthalamide) Polymers 0.000 description 6
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 5
- 239000003365 glass fiber Substances 0.000 description 5
- 239000001361 adipic acid Substances 0.000 description 4
- 235000011037 adipic acid Nutrition 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 229920006119 nylon 10T Polymers 0.000 description 4
- 239000002245 particle Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- REEBJQTUIJTGAL-UHFFFAOYSA-N 3-pyridin-1-ium-1-ylpropane-1-sulfonate Chemical compound [O-]S(=O)(=O)CCC[N+]1=CC=CC=C1 REEBJQTUIJTGAL-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000010128 melt processing Methods 0.000 description 2
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920002490 poly(thioether-sulfone) polymer Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000012745 toughening agent Substances 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
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/36—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with compounds containing nitrogen, e.g. by nitration
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
Abstract
The invention provides a preparation method of a nylon alloy, which comprises the following steps of continuously adding 5-100 parts of polymer, 5-100 parts of diamine and 5-100 parts of diacid and/or diacid ester into a screw extrusion device by mass, uniformly mixing to form a continuously conveyed melt, and feeding the melt into a subsequent polymerization device to form the polymer alloy containing a nylon component. The steps from raw materials to products and energy consumption are reduced, and the product performance is better.
Description
Technical Field
The invention relates to the technical field of engineering plastics, in particular to a preparation method of a nylon alloy.
Background
Nylon is the most common engineering plastic at present, has good mechanical property and temperature resistance, and is widely applied to various aspects of machinery, electrical appliances, electronics, automobiles and the like. However, the application range of the nylon polymer is limited by the defects of high polarity, high water absorption, deformation after water absorption and the like of the nylon polymer. The water absorption of nylon can be reduced by preparing the polyesteramide through copolymerization, but the hydrolysis resistance of the polyester part is far lower than that of the nylon, so that the stability of the polyesteramide material in a high-temperature and high-humidity environment is far inferior to that of the nylon.
Improving polymer properties by melt blending different types of polymers to form polymer alloys is another important way to improve polymer properties. Two or more polymers commonly used to form alloys are incompatible and phase separation occurs when blended. The addition of the compatilizer generally enables various polymers to form a relatively stable micro-phase structure, so as to ensure the stability of the physical properties of the product. In particular, for some nylon polymers with special molecular structures, the melting point or the temperature capable of melt processing is even higher than the decomposition temperature, and the nylon can not be prepared into nylon alloy by the traditional method.
Disclosure of Invention
Aiming at the technical problem, the invention provides a preparation method of a nylon alloy. The polymerization process of nylon and the forming process of alloy are synchronously carried out, so that the steps from raw materials to products and energy consumption are reduced, and the product performance is better.
In order to achieve the purpose of the invention, the invention adopts the technical scheme that:
a preparation method of a nylon alloy comprises the following steps of continuously adding raw materials comprising 5-100 parts by mass of a polymer, 5-100 parts by mass of diamine and 5-100 parts by mass of dibasic acid and/or dibasic acid ester into a screw extrusion device, uniformly mixing to form a continuously conveyed melt, and feeding the melt into a subsequent polymerization device to form the polymer alloy comprising a nylon component.
The nylon alloy raw material of the invention uses diacid and/or diacid ester, diamine small molecule monomer to replace polyamide raw material, the blending reaction contains nylon polymerization reaction, the diacid or ester and diamine monomer are melted and polymerized in a screw extrusion device, the raw material continuously enters screw extrusion equipment, and the polymerization and blending reaction is completed in the flowing process of material transmission, thereby not only realizing the continuity of feeding, reaction and discharging in the small molecule monomer polymerization reaction, overcoming the intermittent production defect of the traditional reaction kettle process, but also omitting the step of preparing nylon salt in aqueous solution, omitting the process of preparing nylon products independently, and directly preparing modified nylon alloy from small molecule monomer through one-step reaction.
The polymer raw material is used as a reactive dispersion medium, and the polymerization monomers are melted, reacted and uniformly mixed in the dispersion medium of the polymer.
The polymer raw material is used as a reactive dispersion medium, the dibasic acid and the diamine meet in a melting dispersion system of the polymer to generate salt, and a polymerization reaction is carried out, so that the whole system is very uniform, the condition that a certain component is incompatible does not occur, and the uniform mixing of the raw materials can be quickly realized.
On the other hand, the dispersion system has a certain melting point and viscosity, and can adapt to the application of screw extrusion equipment, so that the material mixing and dispersing process can be carried out in the screw extrusion equipment, the advantages of high heat transfer and dispersing efficiency of the screw extrusion equipment are fully exerted, the continuous production of small molecular monomer polymerization is realized, and the production efficiency is greatly improved.
The polymer raw material is at least one of polyolefin, polyether, polyphenyl ether, polythioether, polyaromatic hydrocarbon, polystyrene, polysulfone, polysiloxane and vinyl polymer.
Preferably, at least one component of the polymer feedstock contains at least one of amino, carboxyl, anhydride, hydroxyl, epoxy, and oxazoline functionality.
The functional groups have extremely high polarity, can react with amino or carboxyl on nylon, have good binding capacity, can be used as a compatilizer, increase the binding capacity between the raw material polymer and the polymerization generating capacity, and form a stable micro-phase structure.
The polyether, the polythioether and the polysulfone have higher polarity per se and may have certain compatibility with nylon, so that the polar functional group is not necessarily introduced to increase the compatibility, and other polyolefins, polyaromatic hydrocarbons, polystyrene, polysiloxane and vinyl polymers have lower polarity per se and poorer compatibility with nylon, so that the functional group which has higher polarity or can react with nylon is necessarily introduced into at least one component in the polymer raw materials by copolymerization and the like, otherwise, the formed polymer alloy is difficult to achieve higher performance. Even the polymer such as polyether, polythioether and polysulfone can further improve the performance of the alloy by introducing proper functional groups.
The polymer and the diacid and/or diacid ester raw material are melted and mixed uniformly in the screw extrusion device before the diamine is added into the screw extrusion device, and a continuously conveyed melt is formed in the screw extrusion device. In the nylon polymerization process, a large amount of heat is released in the mixing process of diamine and diacid, the temperature of the system far exceeds the boiling point of water, so that water removed in the polymerization reaction forms high-temperature and high-pressure water vapor, therefore, before the diacid and the diamine are mixed, a stable molten mass is formed in a screw extrusion device, and at least one section of a barrel body of the extrusion device is filled with the molten mass, so that water and other volatile raw materials can be sealed in the system. And because the volatility of the dibasic acid is far lower than that of the diamine, the polymer raw material and the dibasic acid monomer are firstly mixed to form a continuously conveyed melt, and then the diamine is added, so that the uncontrollable leakage of high-pressure steam from a raw material inlet can be avoided.
Preferably, the diamine is continuously fed into the screw extrusion apparatus in the form of a liquid or a solution. The tightness of the equipment is easier to ensure.
The subsequent polymerization apparatus of the present invention is a polymerization apparatus for continuous conveyance.
The continuously-conveyed polymerization device is at least one of a screw extrusion device and a tubular reaction device.
The polymer raw materials used in the invention can not be severely degraded under the condition of nylon polymerization, so that the polymer raw materials have higher melt viscosity in the process of material melting and conveying, and in order to ensure sufficient sealing, the proportion of the polymer raw materials in the invention is not less than 2 percent, preferably 5 percent of the mass of the nylon component in the final product.
The molar ratio of the two monomers during the polymerization of the diamine and the diacid to form nylon is generally comparable, since diamines are generally more volatile and will be slightly more abundant than diacids. In the present invention, since the polymer raw material may contain an amino group, a carboxylic acid, or an acid anhydride, and may also participate in the nylon polymerization reaction, it is necessary to take the amount of the amine or the acid into consideration, and the molar ratio of the diamine to the dibasic acid is larger than that in the usual nylon polymerization range, and is adjusted in accordance with the actual situation.
The molar ratio of the dibasic acid and/or dibasic acid ester to the diamine in the raw materials is 0.66-1.5: 1.
the highest temperature reached in the process of preparing the alloy is higher than the decomposition temperature of the nylon component in the product.
Preferably, the diacid raw material contains aromatic diacid, and the molar ratio of the aromatic diacid accounts for at least 20% of the molar ratio of the diacid raw material. The melting point of nylon prepared by the monomer is higher than the decomposition temperature.
The invention has the beneficial effects that:
1. the traditional nylon alloy preparation method is to respectively prepare different polymers, then blend the different polymers, wherein the polymerization process of different raw material polymers needs energy consumption, the process of preparing raw material particles also consumes energy, and then melt and blend the raw material particles, wherein the energy consumption is repeatedly wasted. According to the invention, the micromolecular monomer is used for replacing nylon as a raw material, and the polymerization and blending of the nylon are simultaneous, so that the repeated energy consumption of granulating the nylon from a melt state and then melting the particles can be reduced, and the method has an important significance for saving and reducing emission.
2. The initial material mixture of traditional alloy preparation is the mixture of macromolecule and macromolecule, the molecular chain can twine, it is more difficult to move and disperse, the stage of mixing at first of the invention is the mixture of micromolecule and macromolecule, the micromolecule can enter between the chains of macromolecule, mix more evenly, the physical property is more stable, the performance of products is better.
3. For nylon with melting point or temperature which can be melt-processed and is higher than the decomposition temperature, the nylon alloy can not be prepared by the traditional method, but the melt-processing temperature of the whole material adopting the method can still be below the decomposition temperature of the nylon, and the nylon alloy can still be prepared by the method. Is particularly suitable for the condition that the highest temperature in the preparation process of the alloy is higher than the decomposition temperature of nylon in the product.
Detailed Description
In order to more clearly and specifically illustrate the technical solution of the present invention, the present invention is further described by the following embodiments. The following examples are intended to illustrate the practice of the present invention and are not intended to limit the scope of the invention.
Example 1
A preparation method of a nylon alloy comprises the following steps of continuously adding 5 parts of polymer, 5 parts of diamine and 5 parts of dibasic acid into a screw extrusion device by mass, uniformly mixing to form a continuously conveyed melt, and feeding the melt into a subsequent polymerization device to form the polymer alloy comprising a nylon component.
Example 2
A preparation method of a nylon alloy comprises the following steps of continuously adding 100 parts of polymer, 90 parts of diamine and 90 parts of dibasic acid ester into a screw extrusion device by mass, uniformly mixing to form a continuously conveyed melt, and feeding the melt into a subsequent polymerization device to form the polymer alloy comprising a nylon component.
The polymer raw material is used as a reactive dispersion medium, and the polymerization monomers are melted, reacted and uniformly mixed in the dispersion medium of the polymer.
The polymer raw material is at least one of polyolefin, polyether, polyphenyl ether, polythioether, polyaromatic hydrocarbon, polystyrene, polysulfone, polysiloxane and vinyl polymer.
At least one component of the polymer raw material contains at least one of amino, carboxyl, acid anhydride, hydroxyl, epoxy and oxazoline functional groups.
The molar ratio of the dibasic acid and/or dibasic acid ester to the diamine in the raw materials is 1: 1.
the maximum temperature reached during the preparation of the alloy is higher than the decomposition temperature of the nylon component in the product.
Example 3
A preparation method of a nylon alloy comprises the following steps of continuously adding 50 parts of polymer, 100 parts of diamine and 100 parts of dibasic acid into a screw extrusion device by mass, uniformly mixing to form a continuously conveyed melt, and feeding the melt into a subsequent polymerization device to form the polymer alloy containing a nylon component.
The polymer raw material is used as a reactive dispersion medium, and the polymerization monomers are melted, reacted and uniformly mixed in the dispersion medium of the polymer.
The polymer raw material is at least one of polyolefin, polyether, polyphenyl ether, polythioether, polyaromatic hydrocarbon, polystyrene, polysulfone, polysiloxane and vinyl polymer.
At least one component in the polymer raw material contains at least one of amino, carboxyl, acid anhydride, hydroxyl, epoxy and oxazoline functional groups.
The proportion of the polymer raw material is not less than 2 percent, preferably 5 percent of the mass of the nylon component in the final product.
The molar ratio of the dibasic acid and/or dibasic acid ester to the diamine in the raw materials is 0.66: 1.
the dibasic acid raw material contains aromatic dibasic acid, and the molar ratio of the aromatic dibasic acid accounts for at least 20% of the molar ratio of the dibasic acid raw material.
Example 4
A preparation method of a nylon alloy comprises the following steps of continuously adding 20 parts of polymer, 60 parts of diamine and 50 parts of diacid into a screw extrusion device by mass, uniformly mixing to form a continuously conveyed melt, and feeding the melt into a subsequent polymerization device to form the polymer alloy containing a nylon component.
The polymer raw material is used as a reactive dispersion medium, and the polymerization monomers are melted, reacted and uniformly mixed in the dispersion medium of the polymer.
The polymer raw material is at least one of polyolefin, polyether, polyphenyl ether, polythioether, polyaromatic hydrocarbon, polystyrene, polysulfone, polysiloxane and vinyl polymer.
At least one component of the polymer raw material contains at least one of amino, carboxyl, acid anhydride, hydroxyl, epoxy and oxazoline functional groups.
The polymer raw material and the dibasic acid monomer are firstly mixed to form a continuously conveyed melt, and the diamine is added, so that uncontrollable leakage of high-pressure steam from a raw material inlet can be avoided.
The diamine is continuously fed into the screw extruder in the form of a liquid or solution. The tightness of the device is easier to ensure.
The subsequent polymerization apparatus is a continuously conveyed polymerization apparatus.
The continuously-conveying polymerization device is at least one of a screw extrusion device and a tubular reaction device.
The proportion of the polymer raw material is not less than 2 percent, preferably 5 percent of the mass of the nylon component in the final product.
The molar ratio of the dibasic acid and/or dibasic acid ester to the diamine in the raw materials is 1.5: 1.
the dibasic acid raw material contains aromatic dibasic acid, and the molar ratio of the aromatic dibasic acid accounts for at least 20% of the molar ratio of the dibasic acid raw material.
Example 5
According to the proportion of 20: 10 weight percent of maleic anhydride grafted POE and terephthalic acid, 0.5 percent of antioxidant and 0.2 percent of catalyst which account for the total weight are mixed and are sent into a co-rotating twin-screw extruder from the front end through weight loss metering equipment. Setting the screw temperature, wherein the temperature of a feeding section is 100-: 166. the materials are uniformly mixed in a screw extrusion device and enter a continuous flow reactor with a stirring device, the temperature is controlled to be 280-310 ℃, and the effective volume of the reactor is 50 liters. And continuously flowing the material out of the continuous flow reactor, and then extruding and granulating the material in a co-rotating double-screw extruder with the length-diameter ratio of 48:1 to obtain the PA6T/POE alloy. The average residence time of the material in the polymerization apparatus was 20 minutes.
The melting point of the nylon component PA6T exceeds 370 ℃, the melting point exceeds the decomposition temperature of PA6T, the alloy cannot be directly melt-processed, the alloy cannot be prepared by the traditional method, and the PA6T/POE alloy prepared by the method can be melt-processed within 320 ℃. The water absorption of PA6T/POE is 0.2%, which is much lower than that of PA6T/66, and is 1.2%.
Example 6
According to the following steps of 20: 10 weight percent of GMA branched POE and terephthalic acid, 0.5 percent of antioxidant and 0.2 percent of catalyst in the total weight are mixed and are fed into a co-rotating double-screw extruder from the front end through weight loss metering equipment. Setting the screw temperature, wherein the temperature of a feeding section is 100-: 166. the materials are uniformly mixed in a screw extrusion device and enter a continuous flow reactor with a stirring device, the temperature is controlled to be 280-310 ℃, and the effective volume of the reactor is 50 liters. And continuously flowing the material out of the continuous flow reactor, and then extruding and granulating the material in a co-rotating double-screw extruder with the length-diameter ratio of 48:1 to obtain the PA5T/POE alloy. The average residence time of the material in the polymerization apparatus was 20 minutes.
The melting point of the nylon component PA5T is close to the decomposition temperature of PA5T, the alloy can not be directly melt-processed, the alloy can not be prepared by the traditional method, and the PA5T/POE alloy prepared by the method can be melt-processed within 310 ℃. The water absorption of PA5T/POE was 0.2%, which was much lower than that of PA5T/56, which was 1.3%.
Example 7
According to the proportion of 20: 10, mixing oxazoline branch PP and terephthalic acid, 0.5 percent of antioxidant and 0.2 percent of catalyst in percentage by weight, and feeding the mixture into a co-rotating double-screw extruder from the front end through weight loss metering equipment. Setting the screw temperature, wherein the temperature of a feeding section is 100-: 166. the materials are uniformly mixed in a screw extrusion device and enter a continuous flow reactor with a stirring device, the temperature is controlled to be 280-310 ℃, and the effective volume of the reactor is 50 liters. And continuously flowing the material out of the continuous flow reactor, and then extruding and granulating the material in a co-rotating double-screw extruder with the length-diameter ratio of 48:1 to obtain the PA5T/PP alloy. The average residence time of the material in the polymerization apparatus was 20 minutes.
The melting point of the nylon component PA5T is close to the decomposition temperature of PA5T, the alloy can not be directly melt-processed, the alloy can not be prepared by the traditional method, and the PA5T/PP alloy prepared by the method can be melt-processed within 310 ℃. The water absorption of the PA5T/PP alloy is 0.3 percent and is far lower than that of PA5T/56 by 1.4 percent.
Example 8
According to the following steps of 10: 10: 7.3 PPS, terephthalic acid and adipic acid, an antioxidant accounting for 0.5 percent of the total weight and a catalyst accounting for 0.2 percent of the total weight are mixed and are fed into a co-rotating double-screw extruder from the front end through a weight loss metering device. Setting the screw temperature, wherein the temperature of a feeding section is 150-: 1, the weight is 13 parts, the materials are uniformly mixed in a screw extrusion device and enter a continuous flow reactor with a stirring device, the temperature is controlled to be 280-310 ℃, and the effective volume of the reactor is 50 liters. The material continuously flows out of the continuous flow reactor and enters a co-rotating twin-screw extruder with the length-diameter ratio of 48:1 for extrusion and granulation to obtain PA6T/66/PPS alloy, the average retention time of the material is 20 minutes, the melting point is 305 ℃, and the unnotched impact strength is 33kj/m 2 。
Example 9
30 parts of PPS, 70 parts of PA6T/66 and 0.5% antioxidant are mixed from the aspect ratio of 48:1, adding the mixture into the front end of a double-screw extruder, setting the temperature of each section to be 270-320 ℃, extruding and granulating to obtain PA6T/66/PPS alloy with the melting point of 303 ℃ and the unnotched impact strength of 22kj/m 2 . The average residence time of the material in the polymerization apparatus was 20 minutes.
This example is a traditional nylon alloy preparation method, and example 8 compares with it, and the impact strength has improved 50%, and the alloy that synthesizes is better compatible.
Example 10
According to the weight ratio of 30: 1.5: 10, uniformly mixing PPO, maleic anhydride grafted PS and adipic acid, continuously adding the mixture into an extruder from the front end of a double-screw extrusion device to melt the materials, and then continuously adding liquid hexamethylenediamine into a 7 th barrel, wherein the molar ratio of the hexamethylenediamine to the adipic acid is 1.03: 1, uniformly mixing materials in a screw extrusion device, entering a continuous flow reactor with a stirring device, controlling the temperature at 280-310 ℃, and controlling the effective volume of the reactor at 50 liters.The material continuously flows out of the continuous flow reactor and enters a co-rotating twin-screw extruder with the length-diameter ratio of 48:1, glass fiber accounting for 30 percent of the weight of the resin is continuously added into the cylinder side at the section 6 of the extruder for extrusion granulation, and the glass fiber reinforced PPO/PA66 alloy with the unnotched impact strength of 32kj/m and the notch impact strength of 30 kj/m is obtained 2 And a heat distortion temperature of 182 ℃. The average residence time of the material in the polymerization apparatus was 20 minutes.
In the embodiment, other components such as glass fiber and the like are added in the screw extrusion granulation process, so that a modified product which can be directly applied is prepared in one step.
Example 11
Continuously adding 30 parts of PPO,1.5 parts of maleic anhydride grafted PS and 15 parts of PA66 into the mixture with the length-diameter ratio of 48:1, after the materials are melted, feeding and continuously adding glass fiber accounting for 30 percent of the weight of the resin into the cylinder body side at the 6 th section, controlling the temperature at 250-310 ℃, extruding and granulating to obtain the glass fiber reinforced PPO/PA66 alloy with the notch impact strength of 25kj/m 2 Heat distortion temperature 175 ℃. The average residence time of the material in the polymerization apparatus was 20 minutes.
This example is a conventional nylon alloy preparation method, and example 10 has a significantly improved impact strength and better compatibility with the synthesized alloy.
Example 12
According to the following steps: 10: 7.3 mixing the amino-terminated polysiloxane, the terephthalic acid and the adipic acid according to the weight ratio, 0.5 percent of antioxidant and 0.2 percent of catalyst according to the total weight, and feeding the mixture into a co-rotating double-screw extruder from the front end through a weight loss metering device. Setting the temperature of a screw, wherein the temperature of a feeding section is 150-: 1, 13 parts by weight, uniformly mixing materials in a screw extrusion device, feeding the materials into a continuous flow reactor with a stirring device, controlling the temperature to be 280-310 ℃, and controlling the effective volume of the reactor to be 50 liters. The material continuously flows out of the continuous flow reactor and enters a co-rotating twin-screw extruder with the length-diameter ratio of 48:1 for extrusion and granulation to obtain the PA 6T/66/silica gel alloy, the average retention time of the material is 20 minutes, the water absorption is as low as 0.1 percent and is far lower than that of PA6T/661.5%, notched impact strength 43kj/m 2 。
Example 13
According to the following steps of 10: 15 parts by weight of PPS and terephthalic acid, an antioxidant accounting for 0.5 percent of the total weight, and a catalyst accounting for 0.2 percent of the total weight are mixed and are fed into a co-rotating twin-screw extruder from the front end through a weight loss metering device. Setting the temperature of a screw, wherein the temperature of a feeding section is 150-: 1, the weight is 16 parts, the materials are uniformly mixed in a screw extrusion device and enter a continuous flow reactor with a stirring device, the temperature is controlled to be 280-310 ℃, and the effective volume of the reactor is 50 liters. The material continuously flows out of the continuous flow reactor and enters a co-rotating twin-screw extruder with the length-diameter ratio of 48:1 for extrusion and granulation to obtain PA10T/PPS, the average retention time of the material is 20 minutes, the water absorption is as low as 0.1 percent and is far lower than 0.5 percent of PA10T, and the unnotched impact strength is 43kj/m 2 。
Example 14
According to the following steps: PPS, terephthalic acid and decamethylene diamine are mixed according to the weight ratio of 15:16, an antioxidant accounting for 0.5 percent of the total weight and a catalyst accounting for 0.2 percent of the total weight are fed into a co-rotating double-screw extruder from the front end through a weight loss metering device. The screw temperature is set, the temperature of the feeding section is 150-230 ℃, the temperature of the melting and dispersing section is 270-305 ℃, materials are melted and mixed uniformly and then enter a continuous flow reactor with a stirring device, the temperature is controlled to be 280-310 ℃, and the effective volume of the reactor is 50 liters. The material continuously flows out of the continuous flow reactor and enters a co-rotating twin-screw extruder with the length-diameter ratio of 48:1 for extrusion and granulation to obtain PA10T/PPS, the average retention time of the material is 20 minutes, the water absorption is as low as 0.1 percent and is far lower than 0.5 percent of PA10T, and the unnotched impact strength is 38kj/m 2 。
In this example, the diamine and other raw materials can be added directly from the beginning to prepare the alloy material, which is more convenient for the solid diamine in operation, but the performance of the prepared material is slightly poor because the amine is more easily volatilized and lost. In actual production, the method can be flexibly selected according to equipment and requirements on physical properties of materials.
Example 15
According to the following steps of 20: 5: 10 weight percent of maleic anhydride grafted POE, PA66, terephthalic acid, antioxidant accounting for 0.5 percent of the total weight and catalyst accounting for 0.2 percent of the total weight are mixed and sent into a co-rotating twin-screw extruder from the front end through weight loss metering equipment. Setting the screw temperature, wherein the temperature of a feeding section is 100-: 166. the materials are uniformly mixed in a screw extrusion device and enter a continuous flow reactor with a stirring device, the temperature is controlled to be 280-310 ℃, and the effective volume of the reactor is 50 liters. And continuously flowing the material out of the continuous flow reactor, and then extruding and granulating the material in a co-rotating double-screw extruder with the length-diameter ratio of 48:1 to obtain the PA6T/66/POE alloy. The average residence time of the material in the polymerization apparatus was 20 minutes, and the notched impact strength was 35j/m 2 。
The alloy material polymer prepared by the invention has functional groups capable of reacting with nylon, and the formed alloy has part of polymers and nylon which are covalently bonded together, and at least two polymers are well compatible. Therefore, the ratio of each component in the alloy can be adjusted by polymerization blending with other polymers, so that the adjustment of the polymer performance can be more flexible. The alloy prepared by the invention can also be used as a compatilizer for blending other polymers to enhance the performance of other alloys, and the application field of the material obtained by the invention can be expanded.
The preparation method of the invention can add some or several additives such as conventional antioxidant, catalyst, toughening agent, molecular weight regulator and lubricant for polymerization reaction according to the need, or can directly complete the polymerization reaction without adding additives. The preparation method is suitable for synthesis of various nylon alloys, is not limited to the types listed in the examples, and has wide application range.
The above-mentioned embodiments only express the specific embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (12)
1. A preparation method of nylon alloy is characterized by comprising the following steps: the raw materials comprise, by mass, 5-100 parts of polymer, 5-100 parts of diamine and 5-100 parts of dibasic acid and/or dibasic acid ester, the raw materials are continuously added into a screw extrusion device and uniformly mixed to form a continuously conveyed melt, and the melt enters a subsequent polymerization device to form a polymer alloy comprising a nylon component.
2. The method for preparing a nylon alloy according to claim 1, wherein: the polymer raw material is used as a reactive dispersion medium, and the polymerization monomers are melted, reacted and uniformly mixed in the dispersion medium of the polymer.
3. The method for preparing the nylon alloy according to claim 1, wherein the method comprises the following steps: the polymer raw material is at least one of polyolefin, polyether, polyphenyl ether, polythioether, polyaromatic hydrocarbon, polystyrene, polysulfone, polysiloxane and vinyl polymer.
4. The method for preparing a nylon alloy according to claim 3, wherein: at least one component of the polymer raw material contains at least one of amino, carboxyl, acid anhydride, hydroxyl, epoxy and oxazoline functional groups.
5. The method for preparing a nylon alloy according to claim 1, wherein: the polymer and the diacid and/or diacid ester raw material are melted and mixed evenly in the screw extrusion device before the diamine is added into the screw extrusion device, and a continuously conveyed melt is formed in the screw extrusion device.
6. The method for preparing nylon alloy according to claim 5, wherein the diamine is continuously fed into the screw extrusion apparatus in a liquid state or a solution state.
7. The method for preparing a nylon alloy according to claim 1, wherein the subsequent polymerization apparatus is a continuously-fed polymerization apparatus.
8. The method for producing a nylon alloy according to claim 1, wherein the polymer raw material accounts for not less than 2% by mass of the nylon component in the final product.
9. The method for preparing a nylon alloy according to claim 8, wherein the polymer raw material accounts for not less than 5% by mass of the nylon component in the final product.
10. The method for preparing the nylon alloy according to claim 1, wherein the molar ratio of the dibasic acid and/or dibasic acid ester to the diamine in the raw materials is 0.66-1.5: 1.
11. the method for preparing nylon alloy according to claim 1, wherein the maximum temperature reached during the preparation of the alloy is higher than the decomposition temperature of the nylon component in the product.
12. The method for preparing nylon alloy of claim 11, wherein the diacid raw material contains aromatic diacid, and the mole ratio of the aromatic diacid is at least 20% of the mole ratio of the diacid raw material.
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