CN102898657A - Polyamide thermoplastic elastomer containing nano attapulgite and preparation method of elastomer - Google Patents
Polyamide thermoplastic elastomer containing nano attapulgite and preparation method of elastomer Download PDFInfo
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- CN102898657A CN102898657A CN2012104506901A CN201210450690A CN102898657A CN 102898657 A CN102898657 A CN 102898657A CN 2012104506901 A CN2012104506901 A CN 2012104506901A CN 201210450690 A CN201210450690 A CN 201210450690A CN 102898657 A CN102898657 A CN 102898657A
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Abstract
The invention relates to a polyamide thermoplastic elastomer containing nano attapulgite and a preparation method of the elastomer. The polyamide thermoplastic elastomer is mainly prepared by the following steps of: adding 45-90 parts of lactam, 4.5-9 parts of ring opening agent, 0.2-7 parts of dicarboxylic acid blocking agent and 4-9 parts of attapulgite into a reaction container; performing ring opening and normal pressure polymerization and decompressed polymerization to obtain a polyamide/attapulgite prepolymer under nitrogen protection; and adding polyether the molar of which is the same as that of the dicarboxylic acid blocking agent, and performing normal pressure polymerization and decompressed polymerization to obtain a final product of polyether and polyamide segmented copolymer containing attapulgite in the presence of a catalyst, wherein the polyamide accounts for 45 to 90 percent of the mass of the final product, the polyether accounts for 6 to 46 percent of the mass of the final product, and the attapulgite accounts for 4 to 9 percent of the mass of the final product. The polyamide thermoplastic elastomer containing nano attapulgite has high elasticity and mechanical property of the polyamide thermoplastic elastomer, and the heat resistance and fire resistance of the polyamide thermoplastic elastomer containing nano attapulgite are greatly improved.
Description
Technical field
The present invention relates to a kind of thermoplastic polyamide elastomer that contains nano-attapulgite and preparation method thereof.Be particularly related to a kind of thermoplastic polyamide elastomer that contains nano-attapulgite and polyethers and preparation method thereof, in polymeric amide and polyether block polymerization process, added specifically the Attapulgite nano inorganic material and made the thermoplastic polyamide elastomer that contains nano-attapulgite.
Technical background
Attapulgite claims again polygorskite, attapulgite, is a kind of moisture chain layered magnesium silicate minerals, has 2: 1 special structures, and its typical chemical formula is Si
8Mg
6(OH)
2(OH
2)
44H
2O.It is as a kind of natural nano structure mineral material with nanochannel structure, owing to have very large specific surface area, adsorptivity is excellent; In addition, the Attapulgite light specific gravity, Heat stability is good, cheap, also have very strong sterilization, deodorizing, detoxification, killing ability, have higher wholesomeness.Because Attapulgite has vesicular structure, gas is enclosed in the countless small unconnected spaces, the efficient of transmission of heat by convection is very low, can ignore, the thermal conductance of lagging material mainly exists with thermal conduction and thermal radiation form, and the thermal conductivity coefficient of Attapulgite and gas is little, and particularly the thermal conductivity coefficient of gas is less, so Attapulgite has heat insulation effect and resistance toheat; Again because Attapulgite itself has certain flame retardant resistance, therefore, can make its thermotolerance, mechanical property obtain larger raising although add Attapulgite in the superpolymer, to inflammableness also play certain improvement effect (application [J] of attapulgite in modified-high polymer. the Tianjin chemical industry, 2002,4:26-27).
The method of king's one medium human in-situ polymerization synthesized thermotolerance, good mechanical performance nylon 6/ attapulgite clay nano level composite material (synthetic [J] of nylon 6/ attapulgite clay nano level composite material. synthetic resins and plastics, 1997,14:16).
Thermoplastic polyamide elastomer is that polymeric amide is hard section, with terminal carboxyl polyester or the polyethers block type multipolymer as soft section, has the use temperature height, the characteristics such as heat-resistant aging and chemical-resistant are good, can be used for flexible pipe, wire, cable, automobile, the industries such as electrical equipment, also can be used for the hot melt bonding agent, at sports goods, sealing material, electrical component, automobile component, tubing, sheet material, the application of sheath and spandex fiber is progressively exploitation, its optimum preparation condition and changing-nature and application research also there are a lot (ZL200910200344.6 method for producing polyamide thermoplastic elastomer, ZL200910200343.1PA6 type thermoplastic elastomer and preparation method thereof, the preparation method of ZL200810012834.9 zinc-containing polyether ester amides).
Summary of the invention
The object of the present invention is to provide a kind of thermoplastic polyamide elastomer that contains nano-attapulgite and preparation method thereof, be particularly related to a kind of thermoplastic polyamide elastomer that contains nano-attapulgite and polyethers soft silk and preparation method thereof, in polymeric amide and polyether block polymerization process, added specifically the Attapulgite nano inorganic material and made the thermoplastic polyamide elastomer that contains nano-attapulgite.This thermoplastic polyamide elastomer not only has better elasticity and mechanical property, and thermotolerance and also greatly raising of flame retardant resistance.
A kind of thermoplastic polyamide elastomer that contains nano-attapulgite of the present invention is mainly made by following two steps:
(1) adopts the standby technique of existing polymeric amide hydrolysis legal system, 45～90 parts lactan, 4.5～9 parts of ring opening agents, 0.2～7 part of di-carboxylic acid end-capping reagent and 4～9 parts of Attapulgite are joined in the reaction vessel, under nitrogen protection, slowly be warming up to material from room temperature and melt, stir, be warming up to 200 ℃ of ring-opening reaction 1-2h that are hydrolyzed; Reheat to 240-270 ℃, under the stirring velocity of the pressure of 0.2-0.6MPa and 200-700r/min, react 3-6h; Then, be decompressed to 500-5000Pa, reaction 0.5-2h makes molecular-weight average and is the carboxylated attapulgite in the two ends of 2000-15000/polyamide prepolymer aggressiveness; The input amount of described each material all is to calculate according to the mass fraction, and mass fraction described here refers to the numerical value under the equal unit quality condition, and unit mass is every part quality, as every part be 1 the gram, unit mass is exactly 1 gram/part, and 100 parts just equal 100 grams, and 0.1 part then equals 0.1 gram.
(2) under nitrogen protection, will join in the Attapulgite that the first step makes/polyamide prepolymer polymers with the equimolar polyethers of di-carboxylic acid end-capping reagent, under catalyst action, under the stirring velocity of 240-270 ℃ temperature, 500-1000r/min, react 4-6h; Then, be decompressed to 500-5000Pa, reaction 1-3h; At last, after extraction, drying, make polymeric amide and the polyether block copolymer final product that contains Attapulgite.
In the final product of the described thermoplastic polyamide elastomer that contains nano-attapulgite and polyethers, polymeric amide accounts for 45～90% of final product quality, and polyethers accounts for 6～46% of final product quality, and Attapulgite accounts for 4～9% of final product quality.
Described lactan is one or more in hexanolactam, 11 lactan, the laurolactam.
Described ring opening agent is a kind of of water, hexosamine or two kinds of combinations.
Described di-carboxylic acid end-capping reagent is a kind of in hexanodioic acid, sebacic acid, terephthalic acid or the m-phthalic acid.
Described Attapulgite order number is 1000.
Described polyethers is the dibasic alcohol polyethers of C2-C10, molecular weight ranges 400-8000, preferred 1000-4000.
Described dibasic alcohol polyethers is a kind of in polyoxyethylene glycol, poly-1,3-PD, the poly-BDO.
Described catalyzer is that alkoxide compound, hydrocarbon oxy alkaline metal, organic acid are a kind of, and add-on is 1% of dibasic alcohol polyethers quality.
Attapulgite inorganic nano material among the present invention has played the effect of nucleator, so that polymeric amide and polyether block copolymer have higher Tc, shaping cycle shortens.Because the Attapulgite inorganic nano material is Uniform Dispersion in polymeric amide and polyether block copolymer, the elasticity, the mechanical property that have not only effectively kept thermoplastic polyamide elastomer, and its thermotolerance and flame retardant resistance have been improved, and utilize the existing ripe also polymerization process of the polymeric amide of widespread use to produce, need not to increase equipment investment.The thermoplastic polyamide elastomer shock strength that the present invention contains nano-attapulgite reaches 60～120kJ/m
2, elongation at break 30～300%, heat decomposition temperature are 〉=405 ℃, not only can be used as engineering plastics, also can make fiber through melt spinning.
Embodiment
Below in conjunction with embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.
Embodiment 1
Adopt the standby technique of existing polymeric amide hydrolysis legal system, under nitrogen protection, hexanolactam, 109.6 gram hexosamines, 20.5 gram terephthalic acids and the 64.5 gram Attapulgite of 1080.0 grams are joined in the reaction vessel, slowly be warming up to material from room temperature and melt, stir, be warming up to 200 ℃ of ring-opening reaction 2h that are hydrolyzed; Reheat to 250 ℃, under the stirring velocity of the pressure of 0.6MPa and 200r/min, react 6h; Then, be decompressed to 5000Pa, the reaction 2h make the carboxylated Attapulgite in two ends/polyamide 6 performed polymer; Under nitrogen protection, add again 120.2 gram molecular weights and be 1000 polyoxyethylene glycol (with the mole such as terephthalic acid) and 1.2 tetrabutyl titanates that restrain, under 240 ℃, the stirring velocity of 800r/min, react 6h; Then be decompressed to 5000Pa reaction 3h; Finally by extraction, to make polyamide after the drying be 86.6%, the dibasic alcohol content of polyether is 8.8%, the content of Attapulgite is 4.6% the thermoplastic polyamide elastomer that contains nano-attapulgite, its shock strength reaches 90kJ/m
2, elongation at break 100%, 405 ℃ of heat decomposition temperatures.
Embodiment 2
Adopt the standby technique of existing polymeric amide hydrolysis legal system, under nitrogen protection, with 963.1 the gram 11 lactan, 50.2 the gram water, 9.7 restrain oneself diacid and 109.6 the gram Attapulgite join in the reaction vessel, slowly be warming up to material from room temperature and melt, stir, be warming up to 200 ℃ of ring-opening reaction 1.5h that are hydrolyzed; Reheat to 270 ℃, under the stirring velocity of the pressure of 0.2MPa and 500r/min, react 3h; Then, be decompressed to 1000Pa, the reaction 0.5h make Attapulgite/polymeric amide 11 prepolymers; Under nitrogen protection, add again 244.5 gram molecular weights and be 3000 poly-1,3-PD (with the mole such as hexanodioic acid) and 2.4 and restrain the alkoxide lithiums, under 270 ℃, the stirring velocity of 1000r/min, react 4h; Then be decompressed to 1000Pa reaction 1h; Finally by extraction, to make polyamide after the drying be 73.1%, the dibasic alcohol content of polyether is 18.6%, Attapulgite content is 8.3% the thermoplastic polyamide elastomer that contains nano-attapulgite, its shock strength reaches 115kJ/m
2, elongation at break 139%, 413 ℃ of heat decomposition temperatures.
Embodiment 3
Adopt the standby technique of existing polymeric amide hydrolysis legal system, under nitrogen protection, laurolactam, 60.2 gram water and hexosamine (both quality half and half), 5.0 gram m-phthalic acids and the 10.0 gram Attapulgite of 602.1 grams are joined in the reaction vessel, slowly be warming up to material from room temperature and melt, stir, be warming up to 200 ℃ of ring-opening reaction 1h that are hydrolyzed; Reheat to 260 ℃, under the stirring velocity of the pressure of 0.4MPa and 400r/min, react 4h; Then, be decompressed to 2000Pa, the reaction 1h make Attapulgite/polymeric amide 12 prepolymers; Again under nitrogen protection, add 610.1 gram molecular weights and be 2000 poly-BDO (with the mole such as m-phthalic acid) and 6.1 and restrain calcium acetate/antimony trioxide mixtures, under 260 ℃, the stirring velocity of 1000r/min, react 4h; Then be decompressed to 1000Pa reaction 2h; Finally by extraction, to make polyamide after the drying be 47.1%, the dibasic alcohol content of polyether is 45.5%, Attapulgite content is 7.4% the thermoplastic polyamide elastomer that contains nano-attapulgite, its shock strength reaches 112kJ/m
2, elongation at break 240%, heat decomposition temperature are 428 ℃.
Claims (8)
1. one kind contains thermoplastic polyamide elastomer of nano-attapulgite and preparation method thereof, it is characterized in that the described thermoplastic polyamide elastomer that contains nano-attapulgite is polyethers and the polyamide block copolymer that contains nano-attapulgite, is mainly made by following two steps:
(1) adopts the standby technique of existing polymeric amide hydrolysis legal system, under nitrogen protection, 45～90 parts lactan, 4.5～9 parts of ring opening agents, 0.2～7 part of di-carboxylic acid end-capping reagent and 4～9 parts of Attapulgite are joined in the reaction vessel, be heated to 240-270 ℃, under the stirring velocity of the pressure of 0.2-0.6MPa and 200-700r/min, react 3-6h; Then, be decompressed to 500-5000Pa, reaction 0.5-2h makes molecular-weight average and is the carboxylated attapulgite in the two ends of 2000-15000/polyamide prepolymer aggressiveness; The input amount of described each material all is to calculate according to the mass fraction;
(2) under nitrogen protection, will join in the Attapulgite that the first step makes/polyamide prepolymer polymers with the equimolar polyethers of di-carboxylic acid end-capping reagent, under catalyst action, under the stirring velocity of 240-270 ℃ temperature, 500-1000r/min, react 4-6h; Then, be decompressed to 500-5000Pa, reaction 1-3h; At last, after extraction, drying, make polymeric amide and the polyether block copolymer final product that contains Attapulgite;
In the final product of the described thermoplastic polyamide elastomer that contains nano-attapulgite, polymeric amide accounts for 45～90% of final product quality, and polyethers accounts for 6～46% of final product quality, and Attapulgite accounts for 4～9% of final product quality.
2. lactan as claimed in claim 1 is one or more in hexanolactam, 11 lactan or the laurolactam.
3. ring opening agent as claimed in claim 1 is a kind of of water, hexosamine or two kinds of combinations.
4. di-carboxylic acid end-capping reagent as claimed in claim 1 is a kind of in hexanodioic acid, sebacic acid, terephthalic acid or the m-phthalic acid.
5. Attapulgite order number as claimed in claim 1 is 1000.
6. polyethers as claimed in claim 1 is the dibasic alcohol polyethers, molecular weight ranges 400-8000, preferred 1000-4000.
7. dibasic alcohol polyethers as claimed in claim 6 is a kind of in polyoxyethylene glycol, poly-1,3-PD, the poly-BDO.
8. catalyzer as claimed in claim 1 is that four alkoxide compounds, hydrocarbon oxy alkaline metal, organic acid are a kind of; The catalyzer add-on is 1% of polyethers quality.
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| CN106496572A (en) * | 2016-10-20 | 2017-03-15 | 江苏科技大学 | A kind of 6 elastomer of halogen-free flame-retardant polyamide and its in-situ polymerization method for preparing |
| CN106565953A (en) * | 2016-10-28 | 2017-04-19 | 东华大学 | Preparation method of PA6 system polyamide thermoplastic elastomer |
| CN109705338A (en) * | 2018-11-26 | 2019-05-03 | 东华大学 | A kind of low melting-point PA6 elastomer and preparation method thereof |
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| CN106496572B (en) * | 2016-10-20 | 2020-06-16 | 江苏科技大学 | In-situ preparation method of halogen-free flame-retardant polyamide 6 elastomer |
| CN106565953A (en) * | 2016-10-28 | 2017-04-19 | 东华大学 | Preparation method of PA6 system polyamide thermoplastic elastomer |
| CN106565953B (en) * | 2016-10-28 | 2018-12-04 | 东华大学 | A kind of preparation method of PA6 system thermoplastic polyamide elastomer |
| CN109705338A (en) * | 2018-11-26 | 2019-05-03 | 东华大学 | A kind of low melting-point PA6 elastomer and preparation method thereof |
| CN112011143A (en) * | 2020-07-21 | 2020-12-01 | 杭州联和工具制造有限公司 | Composition for thermoplastic elastomer and application thereof |
| CN112011143B (en) * | 2020-07-21 | 2022-09-16 | 杭州联和工具制造有限公司 | Composition for thermoplastic elastomer and application thereof |
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