CN105860454A - Anti-oxidant pbt material and preparation method thereof - Google Patents
Anti-oxidant pbt material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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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- 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
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2201/011—Nanostructured additives
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Abstract
The invention discloses an anti-oxidant pbt material. The anti-oxidant pbt material is prepared from, by weight, 2-4 parts of pentaerythritol, 1-2 parts of 1,2-benzo isothiazolin-3-ketone, 70-80 parts of caprolactam, 10-13 parts of attapulgite, 1-1.4 parts of zinc acetate, 2-3 parts of gamma-aminopropyltriethoxysilane, 18-20 partsof oxalic acid, 300-370 parts of polybutylene terephthalate, 0.8-1 part of hexamethyl cyclotrisiloxane, 3-4 parts of aluminum dihydrogen phosphate, 1-2 parts of calcium hydrophosphate, 0.6-1 part of thiodipropionicacid dilauryl ester, 1-2 parts of dithio-salicylic acid and 0.01-0.02 part of 96-98% sulfuric acid. The material has excellent anti-oxidation performance, long service life, good weather resistance and a wide application range.
Description
Technical field
The present invention relates to field of material technology, particularly relate to a kind of antioxidation 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 antioxidation pbt material and preparation side thereof
Method.
The present invention is achieved by the following technical solutions:
A kind of antioxidation pbt material, it is made up of the raw material of following weight parts:
Tetramethylolmethane 2-4, BIT 1-2, 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, pregnancy basic ring
Trisiloxanes 0.8-1, aluminium dihydrogen phosphate 3-4, calcium hydrogen phosphate 1-2, thio-2 acid double dodecane ester 0.6-1, dithio bigcatkin willow
The sulphuric acid 0.01-0.02 of acid 1-2,96-98%.
The preparation method of a kind of described antioxidation pbt material, comprises the following steps:
(1) above-mentioned aluminium dihydrogen phosphate is joined in the deionized water of its weight 16-20 times, rise high-temperature and be 70-75 DEG C, insulation
Stir 4-8 minute；
(2) above-mentioned attapulgite is calcined 1-2 hour at 300-350 DEG C, join acidifying 3-5 in the hydrochloric acid of 3-5mol/l little
Time, souring temperature is 20-35 DEG C, precipitation is joined in above-mentioned aluminium dihydrogen phosphate aqueous solution after filtration, stirs 1-2 hour, mistake
Filter, will be dried at being deposited in 80-90 DEG C, wears into fine powder, obtain 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 zinc oxide load powder；
(5) double for above-mentioned thio-2 acid dodecane esters are joined in tetramethylolmethane, stir, add dithio-salicylic acid,
Rise high-temperature and be 70-80 DEG C, drip the sulphuric acid of above-mentioned 96-98%, insulated and stirred 1-2 hour after dropping, add above-mentioned mixing
In the dehydrated alcohol of system weight 70-80 times, addition gamma-aminopropyl-triethoxy-silane under stirring condition, 200-300 rev/min
Stir 4-10 minute, obtain antioxidant silicon alkanol liquid；
(6) by above-mentioned zinc oxide load powder, calcium hydrogen phosphate mixing, joining in antioxidant silicon alkanol liquid, liter high-temperature is 80-
90 DEG C, insulated and stirred 1.7-2 hour, sucking filtration, precipitation is washed 2-3 time, is vacuum dried 20-30 minute at 50-60 DEG C, obtains ammonia
Base modified zinc oxide load powder；
(7) 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；
(8) 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；
(9) 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 and squeezes
Go out machine extrusion, 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；
The material against oxidative superior performance of the present invention, service life is long, and good weatherability is applied widely.
Detailed description of the invention
A kind of antioxidation pbt material, it is made up of the raw material of following weight parts:
Tetramethylolmethane 2,1,2 BITs 1, caprolactam 70, attapulgite 10, zinc acetate 1, γ aminopropyl three ethoxy
Base silane 2, ethanedioic acid 18, polybutylene terephthalate (PBT) 300, hexamethyl cyclotrisiloxane 0.8, aluminium dihydrogen phosphate 3, phosphoric acid
Hydrogen calcium 1, thio-2 acid double dodecane ester 0.6, the sulphuric acid 0.01 of dithio-salicylic acid 1,96%.
The preparation method of a kind of described antioxidation pbt material, comprises the following steps:
(1) being joined by above-mentioned aluminium dihydrogen phosphate in the deionized water of its weight 16 times, rising high-temperature is 70 DEG C, insulated and stirred 4
Minute；
(2) above-mentioned attapulgite is calcined 1 hour at 300 DEG C, join in the hydrochloric acid of 3mol/l and be acidified 3 hours, acidifying temperature
Degree is 20 DEG C, precipitation is joined in above-mentioned aluminium dihydrogen phosphate aqueous solution after filtration, stirs 1 hour, filters, will be deposited in 80 DEG C
Lower dry, wear into fine powder, obtain 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, cooling, obtains zinc oxide load powder；
(5) double for above-mentioned thio-2 acid dodecane esters are joined in tetramethylolmethane, stir, add dithio-salicylic acid,
Rising high-temperature is 70 DEG C, drips the sulphuric acid of above-mentioned 96%, and insulated and stirred 1 hour after dropping adds above-mentioned mixed system weight
In the dehydrated alcohol of 70 times, adding γ aminopropyl triethoxysilane under stirring condition, 200 revs/min are stirred 4 minutes, obtain antioxygen
SiClx alkanol liquid；
(6) by above-mentioned zinc oxide load powder, calcium hydrogen phosphate mixing, joining in antioxidant silicon alkanol liquid, rising high-temperature is 80
DEG C, insulated and stirred 1.7 hours, sucking filtration, precipitation is washed 2 times, is vacuum dried 20 minutes at 50 DEG C, obtains amino modified zinc oxide
Load powder；
(7) 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；
(8) 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；
(9) 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 and squeezes
Go out machine extrusion, through tie rod, cooling, pelletizing, dried, to obtain final product.
Performance test:
Hot strength is 96.2MPa；
Notch impact strength (KJ/m2) 10.15；
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. an antioxidation pbt material, it is characterised in that it is made up of the raw material of following weight parts:
Tetramethylolmethane 2-4, BIT 1-2, 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, pregnancy basic ring
Trisiloxanes 0.8-1, aluminium dihydrogen phosphate 3-4, calcium hydrogen phosphate 1-2, thio-2 acid double dodecane ester 0.6-1, dithio bigcatkin willow
The sulphuric acid 0.01-0.02 of acid 1-2,96-98%.
2. the preparation method of an antioxidation pbt material as claimed in claim 1, it is characterised in that comprise the following steps:
(1) above-mentioned aluminium dihydrogen phosphate is joined in the deionized water of its weight 16-20 times, rise high-temperature and be 70-75 DEG C, insulation
Stir 4-8 minute；
(2) above-mentioned attapulgite is calcined 1-2 hour at 300-350 DEG C, join acidifying 3-5 in the hydrochloric acid of 3-5mol/l little
Time, souring temperature is 20-35 DEG C, precipitation is joined in above-mentioned aluminium dihydrogen phosphate aqueous solution after filtration, stirs 1-2 hour, mistake
Filter, will be dried at being deposited in 80-90 DEG C, wears into fine powder, obtain 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 zinc oxide load powder；
(5) double for above-mentioned thio-2 acid dodecane esters are joined in tetramethylolmethane, stir, add dithio-salicylic acid,
Rise high-temperature and be 70-80 DEG C, drip the sulphuric acid of above-mentioned 96-98%, insulated and stirred 1-2 hour after dropping, add above-mentioned mixing
In the dehydrated alcohol of system weight 70-80 times, addition gamma-aminopropyl-triethoxy-silane under stirring condition, 200-300 rev/min
Stir 4-10 minute, obtain antioxidant silicon alkanol liquid；
(6) by above-mentioned zinc oxide load powder, calcium hydrogen phosphate mixing, joining in antioxidant silicon alkanol liquid, liter high-temperature is 80-
90 DEG C, insulated and stirred 1.7-2 hour, sucking filtration, precipitation is washed 2-3 time, is vacuum dried 20-30 minute at 50-60 DEG C, obtains ammonia
Base modified zinc oxide load powder；
(7) 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；
(8) 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；
(9) 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 and squeezes
Go out machine extrusion, through tie rod, cooling, pelletizing, dried, to obtain final product.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106380987A (en) * | 2016-11-08 | 2017-02-08 | 芜湖市鸿坤汽车零部件有限公司 | Oxidation-resistant antibacterial leather paint and preparation method thereof |
Citations (3)
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|---|---|---|---|---|
| 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 CN201610231216.8A patent/CN105860454A/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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106380987A (en) * | 2016-11-08 | 2017-02-08 | 芜湖市鸿坤汽车零部件有限公司 | Oxidation-resistant antibacterial leather paint and preparation method thereof |
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Application publication date: 20160817 |