CN109354793A - A kind of high-strength PVC medical material and preparation method thereof - Google Patents
A kind of high-strength PVC medical material and preparation method thereof Download PDFInfo
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- CN109354793A CN109354793A CN201811023918.2A CN201811023918A CN109354793A CN 109354793 A CN109354793 A CN 109354793A CN 201811023918 A CN201811023918 A CN 201811023918A CN 109354793 A CN109354793 A CN 109354793A
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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
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/08—Metals
- C08K2003/0806—Silver
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The present invention relates to field of medical materials, and in particular to arrives a kind of high-strength PVC medical material and preparation method thereof.The high-strength PVC medical material, by weight, preparing raw material includes: 100 parts of polyvinyl chloride resins, 20-55 parts of plasticizer, 1-5 parts of lubricants, 1-3 parts of antioxidants, 1-4 parts of heat stabilizers, 2-4 parts of antibacterial agents.The preparation-obtained high-strength PVC medical material of the present invention has excellent tensile strength and impact resistance, and nontoxic, pollution-free, light, wear-resisting, at low cost.
Description
Technical field
The invention belongs to field of medical materials, more particularly it relates to a kind of high-strength PVC medical material and its system
Preparation Method.
Background technique
Polyvinyl chloride resin (PVC) is one of five big general-purpose plastics, and cheap, modified high comprehensive performance, total output is only
Inferior to polyethylene, it is each to be widely used in industry, agricultural, building, electric, communications and transportation, electric power, telecommunication, packaging etc.
Field.
PVC is a kind of medical macromolecular materials that current medical field is most widely used, with resistance to chemical corrosion,
There is very strong resistance to oxidant, reducing agent and strong acid, and be readily produced, be low in cost, is largely used to be infused
In the pipeline products such as device.But stability of the PVC under light, heat effect is poor, under high temperature action or through a long time sunlight exposes
After solarization, discoloration can be decomposed, physical and mechanical property declines rapidly.
And among the prior art, the generally existing some defects of medical material, such as: intensity is inadequate, toughness is bad and
The disadvantages of difference of hardness, therefore the high-strength PVC medical material for providing a kind of independent research has become the urgent demand of people.
Summary of the invention
To solve the above-mentioned problems, the present invention provides a kind of high-strength PVC medical materials, and by weight, preparation is former
Material includes: 100 parts of polyvinyl chloride resins, 20-55 parts of plasticizer, 1-5 parts of lubricants, 1-3 parts of antioxidants, 1-4 parts of heat stabilizers, 2-4
Part antibacterial agent.
As a kind of perferred technical scheme, by weight, the high-strength PVC medical material prepares raw material packet
Include: 100 parts of polyvinyl chloride resins, 25-35 parts of plasticizer, 2-4 parts of lubricants, 1.5-2.5 parts of antioxidants, 2-3 parts of heat stabilizers,
2.5-3.5 parts of antibacterial agents.
As a kind of perferred technical scheme, the degree of polymerization of the polyvinyl chloride resin is 1500-3000.
As a kind of perferred technical scheme, the heat stabilizer is calcium/zinc composite stabilizer.
As a kind of perferred technical scheme, by weight, the raw material for preparing of the PVC medical material further includes 5-8
Part poly(aryl ether ketone).
As a kind of perferred technical scheme, the poly(aryl ether ketone) has side-chain radical.
As a kind of perferred technical scheme, the side-chain radical is the unsaturated carbonyl of C7 or C8.
As a kind of perferred technical scheme, the unsaturated carbonyl is the chloro- 6- heptene acyl group of 6- or the chloro- 7- octene acyl of 7-
Base.
As a kind of perferred technical scheme, the poly(aryl ether ketone) average grain diameter is 50-80 μm.
The second aspect of the invention provides the preparation method of high-strength PVC medical material, and step includes:
(1) polyvinyl chloride resin and various auxiliary agents are proportionally added into high-speed mixer, reach set temperature 10- to material
After 30 minutes, addition poly(aryl ether ketone), mixed at high speed 10-20 minutes, then the premix through being stirred at low speed cooling system；
(2) above-mentioned premix is transported to PVC to bore in double pelletizers, sets extruder along feed opening to mouth mold direction temperature
It is 130~180 DEG C, die temperature is 150-180 DEG C；
(3) blend is obtained after die extrusion, pelletizing, cooling.
The utility model has the advantages that
Using medical PVC material prepared by the present invention, not only there is excellent tensile strength, but also resist with excellent
Impact and surface hardness, in addition, resulting materials use that is nontoxic, pollution-free, light, wear-resisting, extremely meeting medical material
It is required that.
Specific embodiment
It is further clear, complete that the technical characteristic work in technical solution is provided to the present invention With reference to embodiment
Description, not to the limitation of its protection scope.
Word " preferred ", " preferred " in the present invention etc. refer to, can provide in some cases certain beneficial to effect
The embodiment of the present invention of fruit.However, other embodiments are also likely to be preferred under identical circumstances or in the case of other
's.In addition, do not imply that other embodiments are unavailable to the statement of one or more preferred embodiments, be also not intended to by
Other embodiments exclude except the scope of the present invention.
When a numberical range disclosed herein, above range is considered as continuously, and the minimum value including the range and most
Big value and each value between this minimum value and maximum value.Further, when range refers to integer, including the model
Each integer between minimum value and maximum value enclosed.In addition, when providing multiple range Expressive Features or characteristic, Ke Yihe
And the range.In other words, unless otherwise specified, otherwise all ranges disclosed herein are understood to include and are wherein included into
Any and all subrange.For example, should be regarded as including between minimum value 1 and maximum value 10 from the specified range of " 1 to 10 "
Any and all subrange.The Exemplary range of range 1 to 10 include but is not limited to 1 to 6.1,3.5 to 7.8,5.5 to
10 etc..
To solve the above-mentioned problems, the present invention provides a kind of high-strength PVC medical materials, and by weight, preparation is former
Material includes: 100 parts of polyvinyl chloride resins, 20-55 parts of plasticizer, 1-5 parts of lubricants, 1-3 parts of antioxidants, 1-4 parts of heat stabilizers, 2-4
Part antibacterial agent.
In a preferred embodiment, by weight, the high-strength PVC medical material prepares raw material and includes:
100 parts of polyvinyl chloride resins, 25-35 parts of plasticizer, 2-4 parts of lubricants, 1.5-2.5 parts of antioxidants, 2-3 parts of heat stabilizers, 2.5-
3.5 parts of antibacterial agents.
In a kind of preferred embodiment, by weight, the raw material for preparing of the PVC medical material further includes 5-
8 parts of poly(aryl ether ketone).
Polyvinyl chloride resin
Polyvinyl chloride resin, is a kind of high molecular material for replacing a hydrogen atom in polyethylene using a chlorine atom, and carbon is former
Son is zigzag arrangement, and all atoms are connected with σ key, and all carbon atoms are sp3Hydridization belongs to indefiniteness polymer, contains
The microcrystal of crystallinity 5-10%.Polyvinyl chloride resin powder particles are actually that many PVC minuteness particles physically tie one by cream
The aggregation risen.This aggregate particles are usually only 0.1-0.8 microns of primary primary particle with the size that polymerization initial stage is formed
Based on, it is formed containing several aggregate particles by after primary particle agglomeration having a size of 2-10 microns.Technical grade polyvinyl chloride resin is normal
The molecular weight that it is indicated with average degree of polymerization controls the average molecular weight of resin generally by control polymerization temperature.It is general
The average degree of polymerization range of property polyvinyl chloride resin is from 700-1700, and PVC resin with low degree of polymerization is then from 400-600, high polymerization degree
Polyvinyl chloride resin is 1800-8000.
In some embodiments, the degree of polymerization is to measure the index of polymer molecule size.On the basis of number of repeat unit,
Contained number of repeat unit purpose average value i.e. on polymer macromolecule chain, is indicated with n；On the basis of structural unit number, that is, it polymerize
Contained single structure number of unit on object macromolecular chain.Since high polymer is the mixture of the homologue of different molecular weight mostly,
So the degree of polymerization of high polymer refers to its average degree of polymerization.Polymer is by the same of one group of different polymerization degree and different structure form
It is that the mixture of object is formed, therefore the degree of polymerization is unified meter average value.
In some embodiments, the degree of polymerization of the polyvinyl chloride resin is 1500-3000.
Specifically, the degree of polymerization of the polyvinyl chloride resin is 1500,1700,1900,2200,2500,2800,3000.
Polyvinyl chloride resin is bought from ShanghaiChlorine and Alkali Chemical Co Ltd, the degree of polymerization 1500, model in the application are as follows:
P440；The degree of polymerization is 1900, model are as follows: R1069；The degree of polymerization is 2500, model are as follows: SH-200.
Poly(aryl ether ketone)
Heretofore described poly(aryl ether ketone) is the aromatic ring polymer of a kind of ether-containing key and ketonic bond, and main chain is with phenylene two
Side is separately connected ehter bond and ketonic bond is subject to not homotactic repetitive unit and is constituted.
In a preferred embodiment, the poly(aryl ether ketone) has side-chain radical.
In a preferred embodiment, the side-chain radical is the unsaturated carbonyl of C7 or C8.
In a preferred embodiment, the unsaturated carbonyl is the chloro- 6- heptene acyl group of 6- or the chloro- 7- octene acyl of 7-
Base.
In a preferred embodiment, the poly(aryl ether ketone) average grain diameter is 50-80 μm.
In some embodiments, the poly(aryl ether ketone) is after substituted hydroquinone and difluoro benzophenone condensation
Product is thermally treated again to be obtained.
In a preferred embodiment, the preparation method of the substituted hydroquinone includes:
(1) hydroquinone and unsaturated olefin(e) acid are added in round-bottomed flask, BF is added later3·Et2O solution；
(2) it is cooled to room temperature after heating above-mentioned system 25 minutes at 120 DEG C, ice water is then added, uses Et2O extraction, will
Organic phase is successively washed three times with salt, and NaHCO is saturated3It washes three times, merges organic phase, with anhydrous MgSO4Dry, concentration obtains thick
Crude product is recrystallized to give substituted hydroquinone with EtOH by product.
Wherein, the molar ratio of the hydroquinone and unsaturated olefin(e) acid is 1.2:1；The hydroquinone, No. CAS is 123-
31-9；It is described unsaturation olefin(e) acid include the chloro- 6- heptenoic acid (CAS:731773-28-7) of 6-, the chloro- 7- octenoic acid of 7- (CAS:
731773-29-8), it buys from lark prestige Science and Technology Ltd..
In a preferred embodiment, the preparation step of the poly(aryl ether ketone) includes two steps of synthesis and heat treatment
Suddenly.
In a preferred embodiment, the synthesis step of the poly(aryl ether ketone) includes:
(1) 4,4 '-difluoro benzophenones are added in the there-necked flask containing water-taker, solvent sulfolane is added later, with
And the toluene as azeotropy dehydrant；
(2) by above-mentioned system vacuum and exchange nitrogen, 140 DEG C are heated to, is added under agitation above-mentioned substituted to benzene
Diphenol, natrium carbonicum calcinatum, Anhydrous potassium carbonate；
(3) by system vacuum and exchange nitrogen again, 2h is reacted at 140 DEG C, 6h is reacted at 250 DEG C, is existed after reaction
It is cooled to room temperature under nitrogen atmosphere；
(4) acetone is added in system to pour out product dissolution, obtains pulverulent solids, later three times with distillation washing,
Dehydrated alcohol is washed and obtains poly(aryl ether ketone) crude product three times, and Average Particle Diameters are 90-150 μm.
Wherein, described 4,4 '-difluoro benzophenones, substituted hydroquinone, natrium carbonicum calcinatum, Anhydrous potassium carbonate mole
Than for 2:2.4:1:2.Described 4,4 '-difluoro benzophenones, No. CAS is 345-92-6；The sulfolane, No. CAS is 126-33-
0。
In some embodiments, the heat treatment step of the poly(aryl ether ketone) includes:
(1) by weight, 100 parts of above-mentioned poly(aryl ether ketone) crude products are uniformly mixed with 1 part of antioxidant and 0.1 part of white carbon black
It closes；
(2) said mixture is placed into chamber type electric resistance furnace and is heat-treated, heat treatment temperature is 200-250 DEG C, heat
Handling the time is 1-8 hours, obtains the poly(aryl ether ketone) that Average Particle Diameters are 50-80 μm.
Wherein, the antioxidant is antioxidant 1098, and No. CAS is 23128-74-7；The white carbon black CAS is 14464-
46-1；The poly(aryl ether ketone) particle size is measured using Rise-2008 type laser particle analyzer.
Heretofore described poly(aryl ether ketone), the test result of infrared spectroscopy, which is shown, is located at 1240cm-1Vicinity is ehter bond
(Ar-O-Ar) stretching vibration, 1666cm-1The absorption peak of vicinity is the stretching vibration of ketonic bond (C=O).
The application has found that high-strength PVC medical material provided by the invention has preferable physical and mechanical property, inventor
Speculate the possible reason is, joined poly(aryl ether ketone) in formula, its own aromatic ring by ketonic bond and its contraposition on ehter bond it is mutual
Connection, this stable resonant structure make the orbital electron of high level generate preferable delocalization, shape in entire macromolecular
At the more regular strand of structure.Inventor is found surprisingly that the poly(aryl ether ketone) with side-chain radical, so that material is anti-
Impact significantly improves, and the introducing of this side-chain radical can not only improve the tensile strength of material, can also improve material
Elongation at break and surface hardness.In addition, inventor has found by the heat treatment to poly(aryl ether ketone), to the mechanical property of material
It can further generate certain beneficial effect.
Plasticizer
Heretofore described plasticizer is the high molecular material auxiliary agent being industrially widely used, and is added in plastic processing
Add this substance, its flexibility can be made to enhance, be easily worked, legal can be used for industrial use, be used primarily in high molecular material
In.
In some embodiments, the plasticizer is selected from polyester plasticizer, polyol ester system plasticizer, polybasic carboxylic acid
One of ester system plasticizer, phosphate plasticizer are a variety of.
As the example of polyester plasticizer, including but not limited to: by preferred carbon number 2-12, more preferable, carbon number 2-6 two
Carboxylic acid, with preferred carbon number 2-12, more preferable carbon number 2-6 glycol or its (poly-) alkylen oxide adducts made of polyester etc..Wherein
As dicarboxylic acids, succinic acid, adipic acid, decanedioic acid, terephthalic acid (TPA), M-phthalic acid etc. can be enumerated；As glycol, can enumerate
Propylene glycol, 1,3 butylene glycol, 1,4- butanediol, 1,6-HD, ethylene glycol, diethylene glycol, triethylene glycol etc.；Furthermore it is possible to
The hydroxyl of polyester end, carboxyl monocarboxylic acid, single methanol are esterified and blocked.
As the example of polyol ester system plasticizer, including but not limited to: polyalcohol or its (poly-) alkylen oxide adducts with
It is preferred that carbon number 1-12, the monoesters of the monocarboxylic acid of more preferable carbon number 1-6, further preferred carbon number 1-4, diester or three esters etc..Wherein
As polyalcohol, polyethylene glycol, polypropylene glycol, glycerine, above-mentioned glycol etc. can be enumerated；As monocarboxylic acid, acetic acid, third can be enumerated
Acid etc..
As the example of multi-carboxylate system plasticizer, including but not limited to: polybasic carboxylic acid and preferred carbon number 1-12, more excellent
Select carbon number 1-6, the single methanol of further preferred carbon number 1-4 or the monoesters, diester or three esters of its (poly-) alkylen oxide adducts etc..As
Polybasic carboxylic acid can enumerate trimellitic acid, above-mentioned dicarboxylic acids etc..It is wherein used as single methanol, methanol, ethyl alcohol, 1- propyl alcohol, 1- fourth can be enumerated
Alcohol etc.；Specifically, repefral, diethyl phthalate, dibutyl phthalate, adjacent benzene two can be enumerated
The phthalic acid esters such as formic acid dioctyl ester, dibutyl phthalate (DHP), dibenzyl phthalate, BBP(Butyl Benzyl Phthalate；
The trimellitates such as the own ester of tributyl trimellitate, trioctyl trimellitate (TOTM), tri trimellitate；Diisodecyl adipate (DIDA), oneself two
The adipate esters such as sour Off-Shoot-O；The citrates such as acetyl triethyl citrate, tributyl 2-acetylcitrate；Two -2- second of azelaic acid
The azelates such as the own ester of base；The sebacates such as dibutyl sebacate, Diisooctyl Sebacate；Succinic acid and ethylene oxide
Average addition molal quantity be 2-3 polyethylene glycol monomethyl ether (every 1 hydroxyl addition 2-3 moles of ethylene oxide) ester etc..
As the example of phosphate plasticizer, including but not limited to: phosphoric acid adds with above-mentioned single methanol or its (poly-) oxyalkylene
At the monoesters of object, diester or three esters etc..As concrete example, tributyl phosphate, tricresyl phosphate -2- ethylhexyl, tricresyl phosphate can be enumerated
Monooctyl ester, triphenyl phosphate, 2 ethyl hexyl diphenyl phosphate, tricresyl phosphate, three (ethoxyethoxyethyl) phosphates
Deng.
In a preferred embodiment, the plasticizer is tributyl citrate and/or tributyl 2-acetylcitrate.
Antioxidant
In some embodiments, antioxidant is a kind of auxiliary agent generally used in plastic products, and inventor's discovery is anti-
The use of oxidant can not only reduce the thermal oxide of plastics in process, improve chemical stability, can also slow down modeling
Expect flavescence, aging etc. due to caused by illumination and temperature change in use.
In some embodiments, it is anti-oxidant to be selected from phenol antioxidant, phosphorus antioxidants, sulphur class for the antioxidant
One of agent is a variety of.
As the example of phenol antioxidant, including but not limited to: 3,9- bis- [2- [3- (3- tertiary butyl-4-hydroxy -5- first
Base phenyl) propionyloxy] -1,1- dimethylethyloxy] -2,4,8,10- four oxaspiro [5.5] hendecane, four [3- (3,5- bis-
Tert-butyl-hydroxy phenyl) propionic acid] phenolic compounds with spirocyclic ring scaffold such as pentaerythritol ester；1,3,5,-trimethyl -2,4,
6- tri- (3 ', 5 '-di-tert-butyl-4-hydroxyl benzyl) benzene, bis- [3- (3- tert-butyl -5- methyl -4- hydroxy phenyl) propionic acid] three are sweet
Alcohol ester, 4,4 '-thiobis (6- tert-butyl -3- methylphenol), three-(3,5- di-tert-butyl-4-hydroxyl benzyl)-cyamelides
Ester, 1,3,5- tri- (4- tert-butyl -3- hydroxyl -2,6- dimethyl benzyl)-isocyanuric acid ester, bis- [3- (3,5- di-t-butyls -
4- hydroxy phenyl) propionic acid] 1,6-HD ester, thio-two Asia bis- [3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid] 2,2-
Ethyl ester, N, N '-hexylidene bis- (3,5- di-t-butyl -4- hydroxy-hydrocineamides), 1,3,5- trimethyl -2,4,6- three
Bis- [(pungent sulfenyl) the methyl]-o-cresols of (3,5- di-tert-butyl-4-hydroxyl benzyl) benzene, 2,4-, bis- [3- (3,5- di-t-butyl -4-
Hydroxy phenyl) propionic acid] 1,6-HD ester, [3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid stearyl, 2,2 '-Asias
Methyl bis- (4- methyl-6-tert-butylphenols), 4,4 '-butylidenes-bis- (3 methy 6 tert butyl phenol), (the 2- first of 1,1,3- tri-
Base -4- hydroxyl -5- tert-butyl-phenyl) butane, (4- hydroxybenzyl) benzene of 1,3,5- tri- and four [3- (3,5 '-di-t-butyls -4 '-hydroxyl
Base phenylpropionic acid methylene base ester)] methane etc..
As the example of phosphorus antioxidants, including but not limited to: 3,9- bis- (2,6- di-t-butyl -4- methylenedioxy phenoxies
Base) four oxa- -3,9- of -2,4,8,10- two phospha spiral shell [5.5] hendecane, diphosphorous acid diiso decyl pentaerythritol ester, two phosphorous
The bi-ester of phosphite with spirocyclic ring scaffold such as bis- (2,4- di-tert-butyl-phenyl) pentaerythritol esters of acid；2,2 '-di-2-ethylhexylphosphine oxides
(4,6- di-t-butyl -1- phenyl oxygroup) (2- ethylhexyl oxygroup) phosphorus, 6- [3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl)
Propoxyl group] -2,4,8,10- tetra-tert dibenzo [d, f] [1,3,2] dioxaphosphepin cycloheptene, triphenyl phosphite, phosphorous
Sour diphenyl-isodecyl ester, phenyl diisodecyl ester, phosphorous acid 4,4 '-butylidene-bis- (3- methyl-6-tert butyl phenyl two
(tridecyl)) ester, phosphorous acid stearyl, phosphorous acid three (nonyl phenyl) ester, the miscellaneous -10- phospha of 9,10- dihydro-9-oxy
Miscellaneous -10- phospho hetero phenanthrene -10- the oxidation of phenanthrene -10- oxide, 10- (3,5- di-tert-butyl-4-hydroxyl benzyl) -9,10- dihydro-9-oxy
Object, the miscellaneous -10- phospho hetero phenanthrene -10- oxide of 10- decyloxy -9,10- dihydro-9-oxy, phosphorous acid three (2,4- di-tert-butyl-phenyl)
Bis- (2,4- di-tert-butyl-phenyl) esters of ester, phosphorous acid ring four bases of neopentane, bis- (the 2,6- di-t-butyls of phosphorous acid ring four bases of neopentane
Phenyl) ester, phosphorous acid 2,2- di-2-ethylhexylphosphine oxide (4,6- di-tert-butyl-phenyl) octyl ester, phosphorous acid three (2,4- di-tert-butyl-phenyl)
Ester, -4,4 '-two base ester of double phosphonous acid four (2,4- di-tert-butyl-phenyl) [1,1- xenyl], bis- [bis- (1,1- dimethyl of 2,4-
Ethyl) -6- aminomethyl phenyl] ethyl ester, phosphonic acids etc..
As the example of sulphur class antioxidant, including but not limited to: bis- [3- (dodecylthio) propionic acid] bis- ({ [3- of 2,2-
(dodecylthio) propiono] oxygroup } methyl) two base ester of -1,3- propane, 2-mercaptobenzimidazole, 3,3 '-thio-2 acids two
Lauryl Ester, 3,3 '-thio-2 acid, two myristin, 3,3 '-thio-2 acid distearyl base esters, four (3- lauryl is thio
Propionic acid) compound with sulfide based structural such as pentaerythritol ester；2-mercaptobenzimidazole etc..
In a preferred embodiment, the antioxidant is 2,6- di-tert-butyl-4-methy phenol, and No. CAS is
128-37-0 is bought from Shanghai Aladdin biochemical technology limited liability company.
Lubricant
It studies for a long period of time by present inventor, it is found that lubricant has a variety of efficiency in the actual processing of plastics,
Such as when being kneaded, calendering being processed, polymer adhesion barrel can be prevented, inhibits frictional heat generation, reduces and be kneaded torque and load, from
And prevent the heat deterioration of polymer material.In extrusion molding, mobility can be improved, improve polymer material and barrel and mold
Adhesion prevents and reduces retentate, in addition can also improve the appearance and gloss of film.Promote in addition to this it is possible to play melting
Into agent, prevent adhesion with antistatic agent, slipping agent the effects of.
In some embodiments, the lubricant is able to use known lubricant, including but not limited to: liquid stone
Wax, paraffin, oxidized polyethylene wax, lauric acid, myristic acid, palmitinic acid, stearic acid, arachidic acid, behenic acid, montanic acid, hexanol,
Octanol, hexadecanol, octadecanol, behenyl alcohol, 1,2- ethylene glycol, glycerine, polyglycerol, geoceric acid stearyl alcohol ester, Shan Yu
Suan Shan Yu ester, pentaerythrite tristearate, pentaerythritol tetrastearate, glycerol monostearate, glycerine Dan Shan Yu
Acid esters, stearmide, palmitamide, oleamide, methylene bis stearamide, ethylenebisstearamide, calcium stearate,
Zinc stearate, magnesium stearate, lignite wax, silicone oil etc..
In a preferred embodiment, the lubricant is silicone oil.
Heat stabilizer
In some embodiments, the heat stabilizer is able to use known heat stabilizer, including but not limited to: alkaline earth
Metal chloride, hydrotalcite, calcium-zinc-base, epoxy group, organic phosphorous acid ester group, beta-diketon base, zeolite base, mercapto tinbase, Malaysia
Sour tinbase, lauric acid tinbase and barium-zinc based stabilizer etc..
In a preferred embodiment, the heat stabilizer is calcium/zinc composite stabilizer.
Calcium/zinc composite stabilizer used in this application is that zinc stearate and calcium stearate are carried out by weight 1:1.2
The compound stabilizer of compounding.
Inventor's discovery can effectively prevent PVC using calcium/zinc composite stabilizer in the application and make in heat and shearing force etc.
With lower caused degradation, and when the proportion of the calcium/zinc composite stabilizer is zinc stearate and calcium stearate by weight 1:
When 1.2, it can not only play the role of that PVC is delayed to thermally decompose to a certain extent, reduce difficulty of processing, and make the medical material of PVC
Material has good heat resistance.
Antibacterial agent
In some embodiments, the antibacterial agent in inorganic antiseptic, organic antibacterial agent, natural antibacterial agent one
Kind is a variety of.
As the example of inorganic antiseptic, including but not limited to: zinc oxide, ammonium dihydrogen phosphate, lithium carbonate, is received copper oxide
Rice silver or silver ion.
As the example of organic antibacterial agent, including but not limited to: anilid class, imidazoles, thiazoles, isothiazolone spread out
Biology, quaternary ammonium salt, double croak classes, phenols, vanillic aldehyde or ethyl vanillin aldehydes compound.
As the example of natural antibacterial agent, including but not limited to: chitosan, chitosan quaternary amine, mustard, castor oil or mountain
Certain herbaceous plants with big flowers.
In a preferred embodiment, the antibacterial agent is nano silver.
Inventor has found that nano silver is highly sensitive to some microorganisms, even if only adding on a small quantity into PVC medical material, i.e.,
So that PVC medical material has good antimicrobial properties, the microorganisms such as bacterium, the fungi of material surface can be prevented from sending out
It educates, suppress growth of microorganism, be more in line with the requirement of PVC medical material.
The present invention is specifically described below by embodiment, in addition, if without other explanations, it is raw materials used to be all
It is commercially available.
Embodiment
Embodiment 1
Embodiment 1 provides a kind of high-strength PVC medical material, by weight, the high-strength PVC medical material system
Standby raw material includes: 100 parts of polyvinyl chloride resins, 20 parts of plasticizer, 1 part of lubricant, 1 part of antioxidant, 1 part of heat stabilizer, 2 parts of antibacterials
Agent, 5 parts of poly(aryl ether ketone).
The degree of polymerization of the polyvinyl chloride resin is 1500.
The poly(aryl ether ketone) is obtained so that the product after substituted hydroquinone and difluoro benzophenone condensation is thermally treated again
It arrives.
The preparation method of the substituted hydroquinone includes:
(1) hydroquinone and unsaturated olefin(e) acid are added in round-bottomed flask, BF is added later3·Et2O solution；
(2) it is cooled to room temperature after heating above-mentioned system 25 minutes at 120 DEG C, ice water is then added, uses Et2O extraction, will
Organic phase is successively washed three times with salt, and NaHCO is saturated3It washes three times, merges organic phase, with anhydrous MgSO4Dry, concentration obtains thick
Crude product is recrystallized to give substituted hydroquinone with EtOH by product.
Wherein, the molar ratio of the hydroquinone and unsaturated olefin(e) acid is 1.2:1；The unsaturation olefin(e) acid is the chloro- 6- of 6-
Heptenoic acid.
The preparation step of the poly(aryl ether ketone) includes two steps of synthesis and heat treatment.
The synthesis step of the poly(aryl ether ketone) includes:
(1) 4,4 '-difluoro benzophenones are added in the there-necked flask containing water-taker, solvent sulfolane is added later, with
And the toluene as azeotropy dehydrant；
(2) by above-mentioned system vacuum and exchange nitrogen, 140 DEG C are heated to, is added under agitation above-mentioned substituted to benzene
Diphenol, natrium carbonicum calcinatum, Anhydrous potassium carbonate；
(3) by system vacuum and exchange nitrogen again, 2h, 250 DEG C of reaction 6h, after reaction in nitrogen are reacted at 140 DEG C
Atmosphere is cooled to room temperature under enclosing；
(4) acetone is added in system to pour out product dissolution, obtains pulverulent solids, later three times with distillation washing,
Dehydrated alcohol is washed and obtains poly(aryl ether ketone) crude product three times, and Average Particle Diameters are 100 ± 8 μm.
Wherein, described 4,4 '-difluoro benzophenones, substituted hydroquinone, natrium carbonicum calcinatum, Anhydrous potassium carbonate mole
Than for 2:2.4:1:2.
The heat treatment step of the poly(aryl ether ketone) includes:
(1) by weight, 100 parts of above-mentioned poly(aryl ether ketone) crude products are uniformly mixed with 1 part of antioxidant and 0.1 part of white carbon black
It closes；
(2) said mixture is placed into chamber type electric resistance furnace and is heat-treated, heat treatment temperature is 220 DEG C, when processing
Between be 6 hours, obtain poly(aryl ether ketone), Average Particle Diameters are 60 ± 3 μm.
The plasticizer is tributyl citrate.
The lubricant is silicone oil.
The antioxidant is 2,6 di tert butyl 4 methyl phenol.
The heat stabilizer is the mixture of zinc stearate and calcium stearate, weight ratio 1:1.2.
The antibacterial agent is nano silver.
The preparation method of high-strength PVC medical material, step include:
(1) PVC and various auxiliary agents are proportionally added into high-speed mixer, reach set temperature 30 minutes to material
Afterwards, addition poly(aryl ether ketone), mixed at high speed 20 minutes, then the premix through being stirred at low speed cooling system；
(2) above-mentioned premix is transported to PVC to bore in double pelletizers, sets extruder along feed opening to mouth mold direction temperature
It is 150 DEG C, die temperature is 170 DEG C；
(3) blend is obtained after die extrusion, pelletizing, cooling.
Embodiment 2
2 difference from Example 1 of embodiment is that by weight, the high-strength PVC medical material prepares raw material
It include: 100 parts of polyvinyl chloride resins, 55 parts of plasticizer, 5 parts of lubricants, 3 parts of antioxidants, 4 parts of heat stabilizers, 4 parts of antibacterial agents, 8 parts
Poly(aryl ether ketone).
The degree of polymerization of the polyvinyl chloride resin is 1900.
The preparation method of high-strength PVC medical material, step include:
(1) PVC and various auxiliary agents are proportionally added into high-speed mixer, reach set temperature 10 minutes to material
Afterwards, addition poly(aryl ether ketone), mixed at high speed 10 minutes, then the premix through being stirred at low speed cooling system；
(2) above-mentioned premix is transported to PVC to bore in double pelletizers, sets extruder along feed opening to mouth mold direction temperature
It is 130 DEG C, die temperature is 150 DEG C；
(3) blend is obtained after die extrusion, pelletizing, cooling.
Embodiment 3
3 difference from Example 1 of embodiment is that by weight, the high-strength PVC medical material prepares raw material
Include: 100 parts of polyvinyl chloride resins, 25 parts of plasticizer, 2 parts of lubricants, 1.5 parts of antioxidants, 2 parts of heat stabilizers, 2.5 parts of antibacterial agents,
6 parts of poly(aryl ether ketone).
The degree of polymerization of the polyvinyl chloride resin is 2500.
The preparation method of high-strength PVC medical material, step include:
(1) PVC and various auxiliary agents are proportionally added into high-speed mixer, reach set temperature 30 minutes to material
Afterwards, addition poly(aryl ether ketone), mixed at high speed 20 minutes, then the premix through being stirred at low speed cooling system；
(2) above-mentioned premix is transported to PVC to bore in double pelletizers, sets extruder along feed opening to mouth mold direction temperature
It is 180 DEG C, die temperature is 180 DEG C；
(3) blend is obtained after die extrusion, pelletizing, cooling.
Embodiment 4
4 difference from Example 1 of embodiment is that by weight, the high-strength PVC medical material prepares raw material
Include: 100 parts of polyvinyl chloride resins, 35 parts of plasticizer, 4 parts of lubricants, 2.5 parts of antioxidants, 3 parts of heat stabilizers, 3.5 parts of antibacterial agents,
7 parts of poly(aryl ether ketone).
The degree of polymerization of the polyvinyl chloride resin is 1900.
Embodiment 5
5 difference from Example 1 of embodiment is that by weight, the high-strength PVC medical material prepares raw material
Include: 100 parts of polyvinyl chloride resins, 30 parts of plasticizer, 3 parts of lubricants, 2 parts of antioxidants, 2.5 parts of heat stabilizers, 3 parts of antibacterial agents,
6.5 parts of poly(aryl ether ketone).
The degree of polymerization of the polyvinyl chloride resin is 1900.
Embodiment 6
Embodiment 6 provides a kind of high-strength PVC medical material, by weight, the high-strength PVC medical material system
Standby raw material include: 100 parts of polyvinyl chloride resins, 30 parts of plasticizer, 3 parts of lubricants, 2 parts of antioxidants, 2.5 parts of heat stabilizers, 3 parts it is anti-
Microbial inoculum, 6.5 parts of poly(aryl ether ketone).
The degree of polymerization of the polyvinyl chloride resin is 1900.
The poly(aryl ether ketone) is obtained so that the product after substituted hydroquinone and difluoro benzophenone condensation is thermally treated again
It arrives.
The preparation method of the substituted hydroquinone includes:
(1) hydroquinone and unsaturated olefin(e) acid are added in round-bottomed flask, BF is added later3·Et2O solution；
(2) it is cooled to room temperature after heating above-mentioned system 25 minutes at 120 DEG C, ice water is then added, uses Et2O extraction, will
Organic phase is successively washed three times with salt, and NaHCO is saturated3It washes three times, merges organic phase, with anhydrous MgSO4Dry, concentration obtains thick
Crude product is recrystallized to give substituted hydroquinone with EtOH by product.
Wherein, the molar ratio of the hydroquinone and unsaturated olefin(e) acid is 1.2:1；The unsaturation olefin(e) acid is the chloro- 7- of 7-
Octenoic acid.
The preparation step of the poly(aryl ether ketone) includes two steps of synthesis and heat treatment.
The synthesis step of the poly(aryl ether ketone) includes:
(1) 4,4 '-difluoro benzophenones are added in the there-necked flask containing water-taker, solvent sulfolane is added later, with
And the toluene as azeotropy dehydrant；
(2) by above-mentioned system vacuum and exchange nitrogen, 140 DEG C are heated to, is added under agitation above-mentioned substituted to benzene
Diphenol, natrium carbonicum calcinatum, Anhydrous potassium carbonate；
(3) by system vacuum and exchange nitrogen again, 2h, 250 DEG C of reaction 6h, after reaction in nitrogen are reacted at 140 DEG C
Atmosphere is cooled to room temperature under enclosing；
(4) acetone is added in system to pour out product dissolution, obtains pulverulent solids, later three times with distillation washing,
Dehydrated alcohol is washed and obtains poly(aryl ether ketone) crude product three times, and Average Particle Diameters are 100 ± 6 μm.
Wherein, described 4,4 '-difluoro benzophenones, substituted hydroquinone, natrium carbonicum calcinatum, Anhydrous potassium carbonate mole
Than for 2:2.4:1:2.
The heat treatment step of the poly(aryl ether ketone) includes:
(1) by weight, 100 parts of above-mentioned poly(aryl ether ketone) crude products are uniformly mixed with 1 part of antioxidant and 0.1 part of white carbon black
It closes；
(2) said mixture is placed into chamber type electric resistance furnace and is heat-treated, heat treatment temperature is 220 DEG C, heat treatment
Time is 8 hours, obtains poly(aryl ether ketone), and Average Particle Diameters are 60 ± 3 μm.
The plasticizer is tributyl citrate.
The lubricant is silicone oil.
The antioxidant is 2,6 di tert butyl 4 methyl phenol.
The heat stabilizer is the mixture of zinc stearate and calcium stearate, weight ratio 1:1.2.
The antibacterial agent is nano silver.
The preparation method is the same as that of Example 1 for high-strength PVC medical material.
Embodiment 7
Embodiment 7 provides a kind of high-strength PVC medical material, by weight, the high-strength PVC medical material system
Standby raw material include: 100 parts of polyvinyl chloride resins, 30 parts of plasticizer, 3 parts of lubricants, 2 parts of antioxidants, 2.5 parts of heat stabilizers, 3 parts it is anti-
Microbial inoculum, 6.5 parts of poly(aryl ether ketone).
The degree of polymerization of the polyvinyl chloride resin is 1900.
The poly(aryl ether ketone) is obtained so that the product after substituted hydroquinone and difluoro benzophenone condensation is thermally treated again
It arrives.
The preparation method of the substituted hydroquinone includes:
(1) hydroquinone and unsaturated olefin(e) acid are added in round-bottomed flask, BF is added later3·Et2O solution；
(2) it is cooled to room temperature after heating above-mentioned system 25 minutes at 120 DEG C, ice water is then added, uses Et2O extraction, will
Organic phase is successively washed three times with salt, and NaHCO is saturated3It washes three times, merges organic phase, with anhydrous MgSO4Dry, concentration obtains thick
Crude product is recrystallized to give substituted hydroquinone with EtOH by product.
Wherein, the molar ratio of the hydroquinone and unsaturated olefin(e) acid is 1.2:1；The unsaturation olefin(e) acid is the chloro- 7- of 7-
Octenoic acid.
The preparation step of the poly(aryl ether ketone) includes two steps of synthesis and heat treatment.
The synthesis step of the poly(aryl ether ketone) includes:
(1) 4,4 '-difluoro benzophenones are added in the there-necked flask containing water-taker, solvent sulfolane is added later, with
And the toluene as azeotropy dehydrant；
(2) by above-mentioned system vacuum and exchange nitrogen, 140 DEG C are heated to, is added under agitation above-mentioned substituted to benzene
Diphenol, natrium carbonicum calcinatum, Anhydrous potassium carbonate；
(3) by system vacuum and exchange nitrogen again, 2h, 250 DEG C of reaction 6h, after reaction in nitrogen are reacted at 140 DEG C
Atmosphere is cooled to room temperature under enclosing；
(4) acetone is added in system to pour out product dissolution, obtains pulverulent solids, later three times with distillation washing,
Dehydrated alcohol is washed and obtains poly(aryl ether ketone) crude product three times, and Average Particle Diameters are 100 ± 6 μm.
Wherein, described 4,4 '-difluoro benzophenones, substituted hydroquinone, natrium carbonicum calcinatum, Anhydrous potassium carbonate mole
Than for 2:2.4:1:2.
The heat treatment step of the poly(aryl ether ketone) includes:
(1) by weight, 100 parts of above-mentioned poly(aryl ether ketone) crude products are uniformly mixed with 1 part of antioxidant and 0.1 part of white carbon black
It closes；
(2) said mixture is placed into chamber type electric resistance furnace and is heat-treated, heat treatment temperature is 220 DEG C, heat treatment
Time is 3.5 hours, obtains poly(aryl ether ketone), and Average Particle Diameters are 70 ± 3 μm.
The plasticizer is tributyl citrate.
The lubricant is silicone oil.
The antioxidant is 2,6 di tert butyl 4 methyl phenol.
The heat stabilizer is the mixture of zinc stearate and calcium stearate, weight ratio 1:1.2.
The antibacterial agent is nano silver.
The preparation method is the same as that of Example 1 for high-strength PVC medical material.
Comparative example 1
Comparative example 1 provides a kind of high-strength PVC medical material, by weight, the high-strength PVC medical material system
Standby raw material include: 100 parts of polyvinyl chloride resins, 30 parts of plasticizer, 3 parts of lubricants, 2 parts of antioxidants, 2.5 parts of heat stabilizers, 3 parts it is anti-
Microbial inoculum, 6.5 parts of poly(aryl ether ketone).
The degree of polymerization of the polyvinyl chloride resin is 1900.
The poly(aryl ether ketone) is obtained so that the product after substituted hydroquinone and difluoro benzophenone condensation is thermally treated again
It arrives.
The preparation method of the substituted hydroquinone includes:
(1) hydroquinone and unsaturated olefin(e) acid are added in round-bottomed flask, BF is added later3·Et2O solution；
(2) it is cooled to room temperature after heating above-mentioned system 25 minutes at 120 DEG C, ice water is then added, uses Et2O extraction, will
Organic phase is successively washed three times with salt, and NaHCO is saturated3It washes three times, merges organic phase, with anhydrous MgSO4Dry, concentration obtains thick
Crude product is recrystallized to give substituted hydroquinone with EtOH by product.
Wherein, the molar ratio of the hydroquinone and unsaturated olefin(e) acid is 1.2:1；The unsaturation olefin(e) acid is the chloro- 5- of 5-
Hexenoic acid (CAS:731773-27-6) is bought from lark prestige Science and Technology Ltd..
The preparation step of the poly(aryl ether ketone) includes two steps of synthesis and heat treatment.
The synthesis step of the poly(aryl ether ketone) includes:
(1) 4,4 '-difluoro benzophenones are added in the there-necked flask containing water-taker, solvent sulfolane is added later, with
And the toluene as azeotropy dehydrant；
(2) by above-mentioned system vacuum and exchange nitrogen, 140 DEG C are heated to, is added under agitation above-mentioned substituted to benzene
Diphenol, natrium carbonicum calcinatum, Anhydrous potassium carbonate；
(3) by system vacuum and exchange nitrogen again, 2h, 250 DEG C of reaction 6h, after reaction in nitrogen are reacted at 140 DEG C
Atmosphere is cooled to room temperature under enclosing；
(4) acetone is added in system to pour out product dissolution, obtains pulverulent solids, later three times with distillation washing,
Dehydrated alcohol is washed and obtains poly(aryl ether ketone) crude product three times, and Average Particle Diameters are 120 ± 5 μm.
Wherein, described 4,4 '-difluoro benzophenones, substituted hydroquinone, natrium carbonicum calcinatum, Anhydrous potassium carbonate mole
Than for 2:2.4:1:2.
The heat treatment step of the poly(aryl ether ketone) includes:
(1) by weight, 100 parts of above-mentioned poly(aryl ether ketone) crude products are uniformly mixed with 1 part of antioxidant and 0.1 part of white carbon black
It closes；
(2) said mixture is placed into chamber type electric resistance furnace and is heat-treated, heat treatment temperature is 220 DEG C, heat treatment
Time is 5.5 hours, obtains poly(aryl ether ketone), and Average Particle Diameters are 60 ± 3 μm.
The plasticizer is tributyl citrate.
The lubricant is silicone oil.
The antioxidant is 2,6 di tert butyl 4 methyl phenol.
The heat stabilizer is the mixture of zinc stearate and calcium stearate, weight ratio 1:1.2.
The antibacterial agent is nano silver.
The preparation method is the same as that of Example 1 for high-strength PVC medical material.
Comparative example 2
Comparative example 2 provides a kind of high-strength PVC medical material, by weight, the high-strength PVC medical material system
Standby raw material include: 100 parts of polyvinyl chloride resins, 30 parts of plasticizer, 3 parts of lubricants, 2 parts of antioxidants, 2.5 parts of heat stabilizers, 3 parts it is anti-
Microbial inoculum, 6.5 parts of poly(aryl ether ketone).
The degree of polymerization of the polyvinyl chloride resin is 1900.
The poly(aryl ether ketone) is obtained so that the product after substituted hydroquinone and difluoro benzophenone condensation is thermally treated again
It arrives.
The preparation method of the substituted hydroquinone includes:
(1) hydroquinone and unsaturated olefin(e) acid are added in round-bottomed flask, BF is added later3·Et2O solution；
(2) it is cooled to room temperature after heating above-mentioned system 25 minutes at 120 DEG C, ice water is then added, uses Et2O extraction, will
Organic phase is successively washed three times with salt, and NaHCO is saturated3It washes three times, merges organic phase, with anhydrous MgSO4Dry, concentration obtains thick
Crude product is recrystallized to give substituted hydroquinone with EtOH by product.
Wherein, the molar ratio of the hydroquinone and unsaturated olefin(e) acid is 1.2:1；The unsaturation olefin(e) acid is the chloro- 8- of 8-
Nonenoic acid (CAS:731773-30-1) is bought from lark prestige Science and Technology Ltd..
The preparation step of the poly(aryl ether ketone) includes two steps of synthesis and heat treatment.
The synthesis step of the poly(aryl ether ketone) includes:
(1) 4,4 '-difluoro benzophenones are added in the there-necked flask containing water-taker, solvent sulfolane is added later, with
And the toluene as azeotropy dehydrant；
(2) by above-mentioned system vacuum and exchange nitrogen, 140 DEG C are heated to, is added under agitation above-mentioned substituted to benzene
Diphenol, natrium carbonicum calcinatum, Anhydrous potassium carbonate；
(3) by system vacuum and exchange nitrogen again, 2h, 250 DEG C of reaction 6h, after reaction in nitrogen are reacted at 140 DEG C
Atmosphere is cooled to room temperature under enclosing；
(4) acetone is added in system to pour out product dissolution, obtains pulverulent solids, later three times with distillation washing,
Dehydrated alcohol is washed and obtains poly(aryl ether ketone) crude product three times, and Average Particle Diameters are 110 ± 10 μm.
Wherein, described 4,4 '-difluoro benzophenones, substituted hydroquinone, natrium carbonicum calcinatum, Anhydrous potassium carbonate mole
Than for 2:2.4:1:2.
The heat treatment step of the poly(aryl ether ketone) includes:
(1) by weight, 100 parts of above-mentioned poly(aryl ether ketone) crude products are uniformly mixed with 1 part of antioxidant and 0.1 part of white carbon black
It closes；
(2) said mixture is placed into chamber type electric resistance furnace and is heat-treated, heat treatment temperature is 250 DEG C, heat treatment
Time is 3 hours, obtains poly(aryl ether ketone), and Average Particle Diameters are 60 ± 3 μm.
The plasticizer is tributyl citrate.
The lubricant is silicone oil.
The antioxidant is 2,6 di tert butyl 4 methyl phenol.
The heat stabilizer is the mixture of zinc stearate and calcium stearate, weight ratio 1:1.2.
The antibacterial agent is nano silver.
The preparation method is the same as that of Example 1 for high-strength PVC medical material.
Comparative example 3
Comparative example 3 provides a kind of high-strength PVC medical material, by weight, the high-strength PVC medical material system
Standby raw material include: 100 parts of polyvinyl chloride resins, 30 parts of plasticizer, 3 parts of lubricants, 2 parts of antioxidants, 2.5 parts of heat stabilizers, 3 parts it is anti-
Microbial inoculum, 6.5 parts of poly(aryl ether ketone).
The degree of polymerization of the polyvinyl chloride resin is 1900.
The poly(aryl ether ketone) is obtained so that the product after substituted hydroquinone and difluoro benzophenone condensation is thermally treated again
It arrives.
The preparation method of the substituted hydroquinone includes:
(1) hydroquinone and unsaturated olefin(e) acid are added in round-bottomed flask, BF is added later3·Et2O solution；
(2) it is cooled to room temperature after heating above-mentioned system 25 minutes at 120 DEG C, ice water is then added, uses Et2O extraction, will
Organic phase is successively washed three times with salt, and NaHCO is saturated3It washes three times, merges organic phase, with anhydrous MgSO4Dry, concentration obtains thick
Crude product is recrystallized to give substituted hydroquinone with EtOH by product.
Wherein, the molar ratio of the hydroquinone and unsaturated olefin(e) acid is 1.2:1；The unsaturation olefin(e) acid is 7- octenoic acid
(CAS:18719-24-9), it buys from lark prestige Science and Technology Ltd..
The preparation step of the poly(aryl ether ketone) includes two steps of synthesis and heat treatment.The synthesis step of the poly(aryl ether ketone)
Include:
(1) 4,4 '-difluoro benzophenones are added in the there-necked flask containing water-taker, solvent sulfolane is added later, with
And the toluene as azeotropy dehydrant；
(2) by above-mentioned system vacuum and exchange nitrogen, 140 DEG C are heated to, is added under agitation above-mentioned substituted to benzene
Diphenol, natrium carbonicum calcinatum, Anhydrous potassium carbonate；
(3) by system vacuum and exchange nitrogen again, 2h, 250 DEG C of reaction 6h, after reaction in nitrogen are reacted at 140 DEG C
Atmosphere is cooled to room temperature under enclosing；
(4) acetone is added in system to pour out product dissolution, obtains pulverulent solids, later three times with distillation washing,
Dehydrated alcohol is washed and obtains poly(aryl ether ketone) crude product three times, and Average Particle Diameters are 105 ± 10 μm.
Wherein, described 4,4 '-difluoro benzophenones, substituted hydroquinone, natrium carbonicum calcinatum, Anhydrous potassium carbonate mole
Than for 2:2.4:1:2.
The heat treatment step of the poly(aryl ether ketone) includes:
(1) by weight, 100 parts of above-mentioned poly(aryl ether ketone) crude products are uniformly mixed with 1 part of antioxidant and 0.1 part of white carbon black
It closes；
(2) said mixture is placed into chamber type electric resistance furnace and is heat-treated, heat treatment temperature is 220 DEG C, heat treatment
Time is 8 hours, obtains poly(aryl ether ketone), and Average Particle Diameters are 60 ± 3 μm.
The plasticizer is tributyl citrate.
The lubricant is silicone oil.
The antioxidant is 2,6 di tert butyl 4 methyl phenol.
The heat stabilizer is the mixture of zinc stearate and calcium stearate, weight ratio 1:1.2.
The antibacterial agent is nano silver.
The preparation method is the same as that of Example 1 for high-strength PVC medical material.
Comparative example 4
Comparative example 4 provides a kind of high-strength PVC medical material, by weight, the high-strength PVC medical material system
Standby raw material include: 100 parts of polyvinyl chloride resins, 30 parts of plasticizer, 3 parts of lubricants, 2 parts of antioxidants, 2.5 parts of heat stabilizers, 3 parts it is anti-
Microbial inoculum, 6.5 parts of poly(aryl ether ketone).
The degree of polymerization of the polyvinyl chloride resin is 1900.
The poly(aryl ether ketone) is obtained so that the product after substituted hydroquinone and difluoro benzophenone condensation is thermally treated again
It arrives.
The preparation method of the substituted hydroquinone includes:
(1) hydroquinone and unsaturated olefin(e) acid are added in round-bottomed flask, BF is added later3·Et2O solution；
(2) it is cooled to room temperature after heating above-mentioned system 25 minutes at 120 DEG C, ice water is then added, uses Et2O extraction, will
Organic phase is successively washed three times with salt, and NaHCO is saturated3It washes three times, merges organic phase, with anhydrous MgSO4Dry, concentration obtains thick
Crude product is recrystallized to give substituted hydroquinone with EtOH by product.
Wherein, the molar ratio of the hydroquinone and unsaturated olefin(e) acid is 1.2:1；The unsaturation olefin(e) acid is the chloro- 7- of 7-
Octenoic acid.
The preparation step of the poly(aryl ether ketone) includes two steps of synthesis and heat treatment.
The synthesis step of the poly(aryl ether ketone) includes:
(1) 4,4 '-difluoro benzophenones are added in the there-necked flask containing water-taker, solvent sulfolane is added later, with
And the toluene as azeotropy dehydrant；
(2) by above-mentioned system vacuum and exchange nitrogen, 140 DEG C are heated to, is added under agitation above-mentioned substituted to benzene
Diphenol, natrium carbonicum calcinatum, Anhydrous potassium carbonate；
(3) by system vacuum and exchange nitrogen again, 2h, 250 DEG C of reaction 6h, after reaction in nitrogen are reacted at 140 DEG C
Atmosphere is cooled to room temperature under enclosing；
(4) acetone is added in system to pour out product dissolution, obtains pulverulent solids, later three times with distillation washing,
Dehydrated alcohol is washed and obtains poly(aryl ether ketone) crude product three times, and Average Particle Diameters are 100 ± 6 μm.
Wherein, described 4,4 '-difluoro benzophenones, substituted hydroquinone, natrium carbonicum calcinatum, Anhydrous potassium carbonate mole
Than for 2:2.4:1:2.
The heat treatment step of the poly(aryl ether ketone) includes:
(1) by weight, 100 parts of above-mentioned poly(aryl ether ketone) crude products are uniformly mixed with 1 part of antioxidant and 0.1 part of white carbon black
It closes；
(2) said mixture is placed into chamber type electric resistance furnace and is heat-treated, heat treatment temperature is 220 DEG C, heat treatment
Time is 2 hours, obtains poly(aryl ether ketone), and Average Particle Diameters are 90 ± 3 μm.
The plasticizer is tributyl citrate.
The lubricant is silicone oil.
The antioxidant is 2,6 di tert butyl 4 methyl phenol.
The heat stabilizer is the mixture of zinc stearate and calcium stearate, weight ratio 1:1.2.
The antibacterial agent is nano silver.
The preparation method is the same as that of Example 1 for high-strength PVC medical material.
Comparative example 5
Comparative example 5 provides a kind of high-strength PVC medical material, by weight, the high-strength PVC medical material system
Standby raw material include: 100 parts of polyvinyl chloride resins, 30 parts of plasticizer, 3 parts of lubricants, 2 parts of antioxidants, 2.5 parts of heat stabilizers, 3 parts it is anti-
Microbial inoculum, 6.5 parts of poly(aryl ether ketone).
The degree of polymerization of the polyvinyl chloride resin is 1900.
The poly(aryl ether ketone) is obtained so that the product after substituted hydroquinone and difluoro benzophenone condensation is thermally treated again
It arrives.
The preparation method of the substituted hydroquinone includes:
(1) hydroquinone and unsaturated olefin(e) acid are added in round-bottomed flask, BF is added later3·Et2O solution；
(2) it is cooled to room temperature after heating above-mentioned system 25 minutes at 120 DEG C, ice water is then added, uses Et2O extraction, will
Organic phase is successively washed three times with salt, and NaHCO is saturated3It washes three times, merges organic phase, with anhydrous MgSO4Dry, concentration obtains thick
Crude product is recrystallized to give substituted hydroquinone with EtOH by product.
Wherein, the molar ratio of the hydroquinone and unsaturated olefin(e) acid is 1.2:1；The unsaturation olefin(e) acid is the chloro- 7- of 7-
Octenoic acid.
The preparation step of the poly(aryl ether ketone) includes two steps of synthesis and heat treatment.
The synthesis step of the poly(aryl ether ketone) includes:
(1) 4,4 '-difluoro benzophenones are added in the there-necked flask containing water-taker, solvent sulfolane is added later, with
And the toluene as azeotropy dehydrant；
(2) by above-mentioned system vacuum and exchange nitrogen, 140 DEG C are heated to, is added under agitation above-mentioned substituted to benzene
Diphenol, natrium carbonicum calcinatum, Anhydrous potassium carbonate；
(3) by system vacuum and exchange nitrogen again, 2h, 250 DEG C of reaction 6h, after reaction in nitrogen are reacted at 140 DEG C
Atmosphere is cooled to room temperature under enclosing；
(4) acetone is added in system to pour out product dissolution, obtains pulverulent solids, later three times with distillation washing,
Dehydrated alcohol is washed and obtains poly(aryl ether ketone) crude product three times, and Average Particle Diameters are 100 ± 6 μm.
Wherein, described 4,4 '-difluoro benzophenones, substituted hydroquinone, natrium carbonicum calcinatum, Anhydrous potassium carbonate mole
Than for 2:2.4:1:2.
The heat treatment step of the poly(aryl ether ketone) includes:
(1) by weight, 100 parts of above-mentioned poly(aryl ether ketone) crude products are uniformly mixed with 1 part of antioxidant and 0.1 part of white carbon black
It closes；
(2) said mixture is placed into chamber type electric resistance furnace and is heat-treated, heat treatment temperature is 250 DEG C, heat treatment
Time is 6 hours, obtains poly(aryl ether ketone), and Average Particle Diameters are 40 ± 3 μm.
The plasticizer is tributyl citrate.
The lubricant is silicone oil.
The antioxidant is 2,6 di tert butyl 4 methyl phenol.
The heat stabilizer is the mixture of zinc stearate and calcium stearate, weight ratio 1:1.2.
The antibacterial agent is nano silver.
The preparation method is the same as that of Example 1 for high-strength PVC medical material.
Comparative example 6
6 difference from Example 6 of comparative example is the poly(aryl ether ketone) without heat treatment step.
Comparative example 7
7 difference from Example 6 of comparative example is that the poly(aryl ether ketone) is polyether-ether-ketone powder, buys from Changchun Jinlin University
Te Su engineering research Co., Ltd.
Comparative example 8
8 difference from Example 6 of comparative example is: by weight, the high-strength PVC medical material prepares raw material
It include: 100 parts of polyvinyl chloride resins, 30 parts of plasticizer, 3 parts of lubricants, 2 parts of antioxidants, 2.5 parts of heat stabilizers, 3 parts of antibacterial agents, 2
Part poly(aryl ether ketone).
Comparative example 9
9 difference from Example 6 of comparative example is: by weight, the high-strength PVC medical material prepares raw material
It include: 100 parts of polyvinyl chloride resins, 30 parts of plasticizer, 3 parts of lubricants, 2 parts of antioxidants, 2.5 parts of heat stabilizers, 3 parts of antibacterial agents, 15
Part poly(aryl ether ketone).
Performance evaluation
1. tensile property is tested
Tensile strength and elongation at break are tested using universal material experimental machine.Tensile speed is 25cm/min, operation
Temperature is respectively 25 DEG C, 100 DEG C, and sample is tested for the property by GB/T1040-92.
2. notched-impact resistance is tested
Material samples will be blended, impact batten is made according to GB/T1043-93, places 30 hours, eliminate the stress of batten
Afterwards, it is tested for the property with pendulum beam shock machine simply.
3. hardness test
According to GB/T531-2008 test material hardness, thickness of sample 5mm is being more than to be surveyed at 1cm from sample edge
Examination, tests 5 points and is averaged.
1 performance test table of table
By continuing to optimize to experiment condition, embodiment 6 is most preferred embodiment, and at 25 DEG C, the tensile strength of material is broken
It splits elongation, impact resistance and surface hardness and is superior to other embodiments and comparative example.Comparative example 1 and embodiment 6 are carried out
Comparison, tensile strength and impact resistance significantly reduce, and illustrate that side chain lengths shorten so that its mechanical properties decrease.By comparative example
3 compare with embodiment 6, and tensile strength and impact resistance significantly reduce, and illustrate that side-chain radical makes its mechanics without chlorine
Performance decline.By list data it can be found that material still has preferable mechanical property at 100 DEG C of high temperature.
Claims (10)
1. a kind of high-strength PVC medical material, which is characterized in that by weight, prepare raw material include: 100 parts of polyvinyl chloride resins,
20-55 parts of plasticizer, 1-5 parts of lubricants, 1-3 parts of antioxidants, 1-4 parts of heat stabilizers, 2-4 parts of antibacterial agents.
2. high-strength PVC medical material according to claim 1, which is characterized in that by weight, the high intensity
PVC medical material prepare raw material include: 100 parts of polyvinyl chloride resins, 25-35 parts of plasticizer, 2-4 parts of lubricants, 1.5-2.5 parts it is anti-
Oxidant, 2-3 part heat stabilizer, 2.5-3.5 parts of antibacterial agents.
3. high-strength PVC medical material according to claim 1, which is characterized in that the degree of polymerization of the polyvinyl chloride resin is
1500-3000。
4. high-strength PVC medical material according to claim 1, which is characterized in that the heat stabilizer is that calcium/zinc is compound
Stabilizer.
5. high-strength PVC medical material according to claim 1, which is characterized in that by weight, the PVC is medical
The raw material for preparing of material further includes 5-8 parts of poly(aryl ether ketone).
6. high-strength PVC medical material according to claim 5, which is characterized in that the poly(aryl ether ketone) has side chain radical
Group.
7. high-strength PVC medical material according to claim 6, which is characterized in that the side-chain radical is C7's or C8
Unsaturated carbonyl.
8. high-strength PVC medical material according to claim 7, which is characterized in that the unsaturated carbonyl is the chloro- 6- of 6-
Heptene acyl group or the chloro- 7- octenoyl of 7-.
9. high-strength PVC medical material according to claim 5, which is characterized in that the poly(aryl ether ketone) average grain diameter is
50-80μm。
10. the preparation method of the high-strength PVC medical material according to any one of claim 5-9, which is characterized in that
Step includes:
(1) polyvinyl chloride resin and various auxiliary agents are proportionally added into high-speed mixer, reach set temperature 10-30 points to material
Zhong Hou, addition poly(aryl ether ketone), mixed at high speed 10-20 minutes, then the premix through being stirred at low speed cooling system；
(2) above-mentioned premix PVC is transported to bore in double pelletizers, set extruder along feed opening to mouth mold direction temperature as
130~180 DEG C, die temperature is 150-180 DEG C；
(3) blend is obtained after die extrusion, pelletizing, cooling.
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| CN111925609A (en) * | 2020-08-20 | 2020-11-13 | 唐山鸿蕴医疗用品有限公司 | PVC gloves and preparation process thereof |
| CN111925608A (en) * | 2020-08-20 | 2020-11-13 | 唐山鸿蕴医疗用品有限公司 | PVC medical glove and preparation process thereof |
| CN112143130A (en) * | 2020-09-21 | 2020-12-29 | 昆山市金城塑料制品有限公司 | Medical grade material for medical dialysate barrel and preparation process thereof |
| CN114681681A (en) * | 2021-07-07 | 2022-07-01 | 浙江天原医用材料有限公司 | Material for medical catheter and preparation method and application thereof |
| CN115124948A (en) * | 2022-07-08 | 2022-09-30 | 广东时利和汽车材料有限公司 | High-temperature-baking-resistant weld joint sealant and preparation method thereof |
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