CN105860450A - Zinc oxide loaded pbt material and preparation method thereof - Google Patents
Zinc oxide loaded pbt material and preparation method thereof Download PDFInfo
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- CN105860450A CN105860450A CN201610231196.4A CN201610231196A CN105860450A CN 105860450 A CN105860450 A CN 105860450A CN 201610231196 A CN201610231196 A CN 201610231196A CN 105860450 A CN105860450 A CN 105860450A
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- 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
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
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- 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
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
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- C08G69/16—Preparatory processes
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The invention discloses a zinc oxide loaded pbt material. The zinc oxide loaded pbt material is prepared from, by weight, 3-5 parts of benzotriazole, 2-4 parts of glycerin monostearate, 70-80 parts of caprolactam, 10-13 parts of attapulgite, 1-1.4 parts of zinc acetate, 2-3 parts of gamma-ammonia propyl triethoxy silane, 18-20 parts of oxalic acid, 300-370 parts of polybutylene terephthalate, 1-2 parts of coco fatty acid diethanol amide, 10-13 parts of dibutyl maleate, 0.6-1 part of tri-octanoic acid butyltin, 3-4 parts of tricalcium silicate, 2-5 parts of oxidized polyethlene wax, 1-2 parts of lauryl mercaptan and 2-3 parts of calcium stearate. The material can form a micro-network structure with master batch as a core, then, the strength and toughness of a polyamide base material are improved, and the composite material can be dispersed in the polyamide base material better.
Description
Technical field
The present invention relates to field of material technology, particularly relate to a kind of zinc oxide load pbt material and preparation method thereof.
Background technology
ZnO was widely studied in the last few years as a kind of photocatalyst-type anti-biotic agent, and it generates strong oxygen under photocatalysis
The active function groups of the property changed kills antibacterial.It has nontoxic, nonirritant, good stability, and difficult decomposition under high temperature, timeliness is long
For a long time, cheap, the advantage such as aboundresources, have broad application prospects；
The common carrier being presently used for loaded optic catalyst mainly has CNT (CNTs) and activated carbon, mesoporous material, Linesless charcoal
Black and zeolites etc. can obtain the nano-particle of size uniform by load, in turn ensure that functional nano-composites simultaneously
High stability.Nano-photocatalyst/porous mineral compound system, i.e. assembles Nano semiconductor photocatalyst or loads to mineral
In the hole of material or on surface, not only solve the agglomeration traits of nano-photocatalyst granule, reduce its consumption, also simultaneously
Utilize the high-specific surface area of porous mineral, strong characterization of adsorption to realize in water or the targeting enrichment of pollutants in air, urged by light
Agent is more effectively carried out light degradation；
Therefore nano-photocatalyst/porous mineral compound system can improve the disposal efficiency of catalysis material, reduces again
Its consumption and preparation cost, accomplished to have complementary advantages, and this support type composite had both remained the character of nano-particle itself,
Closed by the interface between nano-particle and matrix simultaneously, some new assembly effects can be produced again, make whole complex
System shows as distinctive synergistic enhancing effect, thus significantly improves the functional characteristic of material, but presently used carrier is the most all deposited
In the shortcoming such as expensive, surface activity point is low, therefore, research and develop a kind of novel carrier material and be the most increasingly subject to
The attention of scholars, find a kind of cheap, surface activity is high and the novel carriers of good stability seems the most necessary；
Polyamide due to its good mechanical property, barrier property, anti-wear performance, acid-proof alkaline and good processing characteristics,
Increasingly become indispensable material as engineering plastics and non-fibre material, its application relate to auto parts and components, cord fabric,
The fields such as tyre equatorial, electronic apparatus, household supplies, consumption becomes kinds most in polyamide product.But applying
Cheng Zhong, the polar group of polyamide 6 material makes it be prone to absorb moisture, causes dry state and low temperature impact strength is low, product
Easily there is the phenomenon such as plastic deformation, serious wear in product poor stability, friction, additionally, uses as mine engineering plastics, do not possess
Antistatic property, easily produces gas explosion etc., thus affects the stability of its product size, antiwear and friction reduction property and electrically
Can, which has limited its range of application；
Attapulgite, as a kind of natural nanometer fibrous clay mineral, has 2:1 type layer chain structure, in its crystal structure
There is a large amount of pore passage structure, and have that specific surface area is big, surface activity site is many, energy of adsorption
By force, excellent biocompatibility and the chemically and thermally feature such as stability, be a kind of economical and practical carrier material, giving birth to
The aspects such as thing, environment, new material have broad application prospects；Therefore it is an object of the invention to nano-photocatalyst with recessed
Convex rod stone is effectively combined, and is the most effectively distributed in polyamide, prepares a kind of novel composite.
Summary of the invention
The object of the invention is contemplated to make up the defect of prior art, it is provided that a kind of zinc oxide load pbt material and system thereof
Preparation Method.
The present invention is achieved by the following technical solutions:
A kind of zinc oxide loads pbt material, and it is made up of the raw material of following weight parts:
Benzotriazole 3-5, glyceryl monostearate 2-4, caprolactam 70-80, attapulgite 10-13, zinc acetate 1-1.4,
Gamma-aminopropyl-triethoxy-silane 2-3, ethanedioic acid 18-20, polybutylene terephthalate (PBT) 300-370, coconut oil diethanol
Amide 1-2, dibutyl maleate 10-13, three octanoic acid butyl tin 0.6-1, tricalcium silicate 3-4, OPE 2-5,
Lauryl mercaptan 1-2, calcium stearate 2-3.
The preparation method of a kind of described zinc oxide load pbt material, comprises the following steps:
(1) attapulgite is calcined 1-2 hour at 300-350 DEG C, joins in the hydrochloric acid of 3-5mol/l and be acidified 3-5 hour,
Souring temperature is 20-35 DEG C, precipitation is washed 3-4 time after filtration, is dried, wears into fine powder, obtain pre-treatment and activation at 80-90 DEG C
Attapulgite powder；
(2) above-mentioned benzotriazole is joined in the deionized water of its weight 5-7 times, stir, add tricalcium silicate, rise
High-temperature is 80-90 DEG C, adds above-mentioned pre-treatment and activation attapulgite powder, and insulated and stirred to water is done, and obtains activation attapulgite powder；
(3) take the 16-20% of above-mentioned ethanedioic acid weight, join in the dehydrated alcohol of its weight 25-30 times, stir；
(4) above-mentioned zinc acetate is joined in its weight 70-80 times, 46-50% ethanol solution, add above-mentioned activation concavo-convex
Rod soil powder, ultrasonic 10-20 minute, drips the ethanol solution of above-mentioned ethanedioic acid, magnetic agitation 3-4 minute after dropping, sucking filtration,
Product after sucking filtration is dried 3-5 hour at 110-116 DEG C, sends in Muffle furnace, at 600-640 DEG C, calcine 1.7-2 little
Time, cooling, obtain pretreatment zinc oxide load powder；
(5) above-mentioned lauric acid amide of ethanol is joined in the deionized water of its weight 30-40 times, add calcium stearate, rise
High-temperature is 60-70 DEG C, adds above-mentioned pretreatment zinc oxide load powder, and 70-100 rev/min is stirred 10-16 minute, filters, will
Precipitation is dried at normal temperatures, obtains zinc oxide load powder；
(6) above-mentioned OPE is joined in the dehydrated alcohol of its weight 6-7 times, be sent to the oil bath of 110-120 DEG C
In, insulated and stirred 4-10 minute, discharging, add above-mentioned glyceryl monostearate, stirring, to room temperature, obtains alcohol dispersion liquid；
(7) above-mentioned zinc oxide load powder is joined in the dehydrated alcohol of its weight 60-70 times, add γ-aminopropyl three second
TMOS, rises high-temperature and is 80-90 DEG C, and insulated and stirred 1.7-2 hour adds above-mentioned alcohol dispersion liquid, 80-100 rev/min of stirring
3-4 minute, sucking filtration, precipitation is washed 2-3 time, is vacuum dried 20-30 minute at 50-60 DEG C, obtain amino modified zinc oxide and bear
Carry powder；
(8) take the 10-16% of above-mentioned caprolactam weight, the 20-30% of residue ethanedioic acid weight, load with amino modified zinc oxide
Powder mixes, and adds the distilled water of compound weight 8-10 times, is sent in reactor, rises high-temperature and is 190-200 DEG C, insulation
React 3-4 hour, slowly cool to room temperature, be filtered to remove filtrate, precipitation is dried, grinds to form fine powder, obtain pre-polymerization modified oxidized
Zinc load powder；
(9) above-mentioned pre-polymerization modified zinc oxide load powder is mixed with remaining caprolactam, add compound weight 4-7 times
Distilled water, is sent in reactor, rises high-temperature and is 200-230 DEG C, adds remaining ethanedioic acid, insulation reaction 3-3.5 hour,
Discharging cools down, and is vacuum dried 1-2 hour at 50-60 DEG C, obtains polymeric modification zinc oxide load powder；
(10) being mixed with remaining each raw material by above-mentioned polymeric modification zinc oxide load powder, high-speed stirred is uniform, sends into twin screw
Extruder is extruded, and through tie rod, cooling, pelletizing, dried, to obtain final product.
The invention have the advantage that first attapulgite is calcined and acidification by the present invention, attapulgite can be increased
The silicone hydroxyl group on stone surface, gives attapulgite surface more negative charge, increases its absorbability to metal cation,
By the attapulgite in-situ precipitate of absorption Zn2+ ion is obtained presoma, obtain ZnO/ attapulgite composite wood by calcination
Material, with attapulgite as carrier, can improve the dispersibility of ZnO nanoparticle, it is thus achieved that have the composite of high antibacterial activity,
Attapulgite as layer chain silicate clay, the advantages such as tool specific surface area is big and lateral reactivity site is many, load nano-ZnO
After, considerably increasing the contact area of ZnO and microorganism, high adsorption activity based on attapulgite, antibacterial can be by antibacterial material
Material absorption is forming enrichment about so that ZnO nano granule is easier to directly contact with antibacterial, thus plays its antibacterial characteristics
Cause inactivation of bacteria, then this composite is participated in the pre-polymerization process of caprolactam, utilize caprolactam open-loop products
Aminocaproic acid reacts with the amino of composite material surface, makes composite material surface be grafted a certain amount of polyamide prepolymer aggressiveness, at it
Surface forms one layer of strong boundary layer；Participate in the polymerization process of polyamide the most again, due to the polyamides of composite material surface grafting
Amine performed polymer can participate in the ring-opening polymerisation of caprolactam, therefore, it is possible to form " micronetwork " structure with masterbatch as core, enters
And add intensity and the toughness of polyamide substrate material, and, beneficially composite is in the dispersion of polyamide substrate material.
Detailed description of the invention
A kind of zinc oxide loads pbt material, and it is made up of the raw material of following weight parts:
Benzotriazole 3, glyceryl monostearate 2, caprolactam 70, attapulgite 10, zinc acetate 1, γ aminopropyl three ethoxy
Base silane 2, ethanedioic acid 18, polybutylene terephthalate (PBT) 300, lauric acid amide of ethanol 1, dibutyl maleate
10, three octanoic acid butyl tin 0.6, tricalcium silicate 3, OPE 2, lauryl mercaptan 1, calcium stearate 2.
The preparation method of a kind of described zinc oxide load pbt material, comprises the following steps:
(1) being calcined 1 hour at 300 DEG C by attapulgite, join in the hydrochloric acid of 3mol/l and be acidified 3 hours, souring temperature is
20 DEG C, after filtration, precipitation is washed 3 times, be dried at 80 DEG C, wear into fine powder, obtain pre-treatment and activation attapulgite powder；
(2) above-mentioned benzotriazole is joined in the deionized water of its weight 5 times, stir, add tricalcium silicate, raise
Temperature is 80 DEG C, adds above-mentioned pre-treatment and activation attapulgite powder, and insulated and stirred to water is done, and obtains activation attapulgite powder；
(3) take the 16% of above-mentioned ethanedioic acid weight, join in the dehydrated alcohol of its weight 25 times, stir；
(4) above-mentioned zinc acetate is joined in its weight 70 times, the ethanol solution of 46%, adds above-mentioned activation attapulgite powder,
Ultrasonic 10 minutes, dripping the ethanol solution of above-mentioned ethanedioic acid, magnetic agitation 3 minutes after dropping, sucking filtration, by the product after sucking filtration
Thing is dried 3 hours at 110 DEG C, sends in Muffle furnace, calcines 1.7 hours at 600 DEG C, and cooling obtains pretreatment zinc oxide and bears
Carry powder；
(5) above-mentioned lauric acid amide of ethanol is joined in the deionized water of its weight 30 times, add calcium stearate, rise high temperature
Degree is 60 DEG C, adds above-mentioned pretreatment zinc oxide load powder, and 70 revs/min are stirred 10 minutes, filter, precipitation are done at normal temperatures
Dry, obtain zinc oxide load powder；
(6) above-mentioned OPE is joined in the dehydrated alcohol of its weight 6 times, be sent in the oil bath of 110 DEG C, insulation
Stirring 4 minutes, discharging, add above-mentioned glyceryl monostearate, stirring, to room temperature, obtains alcohol dispersion liquid；
(7) above-mentioned zinc oxide load powder is joined in the dehydrated alcohol of its weight 60 times, add γ aminopropyl-triethoxy
Silane, rising high-temperature is 80 DEG C, insulated and stirred 1.7 hours, adds above-mentioned alcohol dispersion liquid, and 80 revs/min are stirred 3 minutes, sucking filtration, will
Precipitation washing 2 times, is vacuum dried 20 minutes at 50 DEG C, obtains amino modified zinc oxide load powder；
(8) take the 10% of above-mentioned caprolactam weight, the 20% of residue ethanedioic acid weight, mix with amino modified zinc oxide load powder
Closing, add the distilled water of compound weight 8 times, be sent in reactor, rising high-temperature is 190 DEG C, and insulation reaction 3 hours is slow
Slow cool down, to room temperature, is filtered to remove filtrate, precipitation is dried, grinds to form fine powder, obtains pre-polymerization modified zinc oxide load powder；
(9) above-mentioned pre-polymerization modified zinc oxide load powder is mixed with remaining caprolactam, add the steaming of compound weight 4 times
Distilled water, is sent in reactor, and rising high-temperature is 200 DEG C, adds remaining ethanedioic acid, insulation reaction 3 hours, and discharging cools down,
It is vacuum dried 1 hour at 50 DEG C, obtains polymeric modification zinc oxide load powder；
(10) being mixed with remaining each raw material by above-mentioned polymeric modification zinc oxide load powder, high-speed stirred is uniform, sends into twin screw
Extruder is extruded, and through tie rod, cooling, pelletizing, dried, to obtain final product.
Performance test:
Hot strength is 97.3MPa；
Notch impact strength (KJ/m2) 10.07；
Vertical combustion (1.6mm) FV-O；
The zinc oxide load powder wherein prepared is O.lg/L to colibacillary minimum inhibitory concentration.
Claims (2)
1. a zinc oxide load pbt material, it is characterised in that it is made up of the raw material of following weight parts:
Benzotriazole 3-5, glyceryl monostearate 2-4, caprolactam 70-80, attapulgite 10-13, zinc acetate 1-1.4,
Gamma-aminopropyl-triethoxy-silane 2-3, ethanedioic acid 18-20, polybutylene terephthalate (PBT) 300-370, coconut oil diethanol
Amide 1-2, dibutyl maleate 10-13, three octanoic acid butyl tin 0.6-1, tricalcium silicate 3-4, OPE 2-5,
Lauryl mercaptan 1-2, calcium stearate 2-3.
2. the preparation method of a zinc oxide as claimed in claim 1 load pbt material, it is characterised in that include following step
Rapid:
(1) attapulgite is calcined 1-2 hour at 300-350 DEG C, joins in the hydrochloric acid of 3-5mol/l and be acidified 3-5 hour,
Souring temperature is 20-35 DEG C, precipitation is washed 3-4 time after filtration, is dried, wears into fine powder, obtain pre-treatment and activation at 80-90 DEG C
Attapulgite powder；
(2) above-mentioned benzotriazole is joined in the deionized water of its weight 5-7 times, stir, add tricalcium silicate, rise
High-temperature is 80-90 DEG C, adds above-mentioned pre-treatment and activation attapulgite powder, and insulated and stirred to water is done, and obtains activation attapulgite powder；
(3) take the 16-20% of above-mentioned ethanedioic acid weight, join in the dehydrated alcohol of its weight 25-30 times, stir；
(4) above-mentioned zinc acetate is joined in its weight 70-80 times, 46-50% ethanol solution, add above-mentioned activation concavo-convex
Rod soil powder, ultrasonic 10-20 minute, drips the ethanol solution of above-mentioned ethanedioic acid, magnetic agitation 3-4 minute after dropping, sucking filtration,
Product after sucking filtration is dried 3-5 hour at 110-116 DEG C, sends in Muffle furnace, at 600-640 DEG C, calcine 1.7-2 little
Time, cooling, obtain pretreatment zinc oxide load powder；
(5) above-mentioned lauric acid amide of ethanol is joined in the deionized water of its weight 30-40 times, add calcium stearate, rise
High-temperature is 60-70 DEG C, adds above-mentioned pretreatment zinc oxide load powder, and 70-100 rev/min is stirred 10-16 minute, filters, will
Precipitation is dried at normal temperatures, obtains zinc oxide load powder；
(6) above-mentioned OPE is joined in the dehydrated alcohol of its weight 6-7 times, be sent to the oil bath of 110-120 DEG C
In, insulated and stirred 4-10 minute, discharging, add above-mentioned glyceryl monostearate, stirring, to room temperature, obtains alcohol dispersion liquid；
(7) above-mentioned zinc oxide load powder is joined in the dehydrated alcohol of its weight 60-70 times, add γ-aminopropyl three second
TMOS, rises high-temperature and is 80-90 DEG C, and insulated and stirred 1.7-2 hour adds above-mentioned alcohol dispersion liquid, 80-100 rev/min of stirring
3-4 minute, sucking filtration, precipitation is washed 2-3 time, is vacuum dried 20-30 minute at 50-60 DEG C, obtain amino modified zinc oxide and bear
Carry powder；
(8) take the 10-16% of above-mentioned caprolactam weight, the 20-30% of residue ethanedioic acid weight, load with amino modified zinc oxide
Powder mixes, and adds the distilled water of compound weight 8-10 times, is sent in reactor, rises high-temperature and is 190-200 DEG C, insulation
React 3-4 hour, slowly cool to room temperature, be filtered to remove filtrate, precipitation is dried, grinds to form fine powder, obtain pre-polymerization modified oxidized
Zinc load powder；
(9) above-mentioned pre-polymerization modified zinc oxide load powder is mixed with remaining caprolactam, add compound weight 4-7 times
Distilled water, is sent in reactor, rises high-temperature and is 200-230 DEG C, adds remaining ethanedioic acid, insulation reaction 3-3.5 hour,
Discharging cools down, and is vacuum dried 1-2 hour at 50-60 DEG C, obtains polymeric modification zinc oxide load powder；
(10) being mixed with remaining each raw material by above-mentioned polymeric modification zinc oxide load powder, high-speed stirred is uniform, sends into twin screw
Extruder is extruded, and through tie rod, cooling, pelletizing, dried, to obtain final product.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101444717A (en) * | 2008-12-05 | 2009-06-03 | 江苏工业学院 | Method for preparing concavo-convex rod soil/zinc oxide nanometer composite material |
| CN102952327A (en) * | 2011-08-25 | 2013-03-06 | 上海杰事杰新材料(集团)股份有限公司 | Resin composite material and its preparation method and use |
| CN104448299A (en) * | 2013-09-24 | 2015-03-25 | 骏马化纤股份有限公司 | In-situ-polymerized halogen-free flame-retardant nylon 6/attapulgite nano composite material and preparation method thereof |
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2016
- 2016-04-14 CN CN201610231196.4A patent/CN105860450A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101444717A (en) * | 2008-12-05 | 2009-06-03 | 江苏工业学院 | Method for preparing concavo-convex rod soil/zinc oxide nanometer composite material |
| CN102952327A (en) * | 2011-08-25 | 2013-03-06 | 上海杰事杰新材料(集团)股份有限公司 | Resin composite material and its preparation method and use |
| CN104448299A (en) * | 2013-09-24 | 2015-03-25 | 骏马化纤股份有限公司 | In-situ-polymerized halogen-free flame-retardant nylon 6/attapulgite nano composite material and preparation method thereof |
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