CN103965564A - Plasticized polyvinyl chloride material and preparation method thereof - Google Patents
Plasticized polyvinyl chloride material and preparation method thereof Download PDFInfo
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- CN103965564A CN103965564A CN201310030898.2A CN201310030898A CN103965564A CN 103965564 A CN103965564 A CN 103965564A CN 201310030898 A CN201310030898 A CN 201310030898A CN 103965564 A CN103965564 A CN 103965564A
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Abstract
The present invention relates to a novel and non-toxic plasticized polyvinyl chloride material, which comprises A) 100 parts by weight of a PVC resin, B) 20-80 parts by weight of one or a plurality of main plasticizers selected from cyclohexane-1,2-diformate diisooctyl, cyclohexane-1,2-diformate diisononyl, tributyl citrate and acetyl tributyl citrate, and C) 5-20 parts by weight of an ethylene-vinyl acetate-carbonyl copolymer adopted as an auxiliary plasticizer. The material has characteristics of no toxicity, environmental protection, no plasticizer emigration phenomenon, good transparency, suitable processing temperature and excellent comprehensive mechanical property, and can be widely used in the field of food packaging, medical devices and the like. The present invention further relates to a preparation method of the plasticized polyvinyl chloride material, and an application of the plasticized polyvinyl chloride material in food packaging and medical devices.
Description
Technical field
The present invention relates to a kind of plasticized polyvinyl chloride material, this material non-toxic, can, in the widespread use of the field such as food product pack, medicine equipment, be particularly useful for food pack and film, tubing, infusion bag, blood transfusion tube, transfusion bags.The invention still further relates to the preparation method and application of described material.
Background technology
Polyvinyl chloride (being below sometimes called for short PVC) class material has a wide range of applications in medical facilities, and major cause is that polyvinyl chloride material itself has good physical properties.Particularly, these physical propertiess comprise: good consistency between the accessibility of PVC materials processing and this class material and intravenous fluid and blood.The inherent nature such as hardness, flexibility of pure PVC material can be improved by the interpolation of softening agent.The effect of softening agent is: the accessibility that increases flexibility, elongation or the processing (processing) of polymkeric substance.
Aspect medical treatment and nursing, for example, in (: intravenous injection bags of blood, intravenous tube, kidney machine reticular tissue conduit, bubbling type oxygenator, enema drainage bag and urethral catheterization drainage bag) common used PVC series products, all contain dihexyl phthalate (below sometimes vehicle economy HP) softening agent.DEHP is as one of most economical effective and widely used softening agent, and its effect is to make PVC to have flexibility and flexibility.
But, discovered in recent years, the phthalic ester plasticizers such as DEHP in use can leach phenomenon, cause patient to take in or absorb a certain amount of such softening agent.Once but the absorption that produces phthalate plasticizers it has been generally acknowledged that these softening agent can be stored in fatty tissue and can cause deformity.People also suspect that DEHP can cause endocrine disorder, affect the health of reproductive system, affect the health of pregnant woman and ewborn infant, and extremely have certain relation with male genetic road.Many countries, such softening agent is taked to certain measure one after another: European Union and the U.S. forbid that toy for children below 3 years old and articles for use use phthalic ester plasticizer, Japan forbids adding such softening agent in medicine equipment related products, and China has also taked some restrictions to such softening agent at present.
Therefore, be badly in need of at present adopting the softening agent of novel asepsis environment-protecting to carry out modification to PVC.Patent DE29824628 and WO99/32427 disclose hexanaphthene-1 by prepared by corresponding phthalic acid ester hydrogenation, 2-dicarboxylic ester softening agent, such softening agent has lower density and viscosity, causes the low-temperature pliability of plastics to make moderate progress than corresponding phthalic ester.Also the mechanical property that has its gained plastics of literature review with obtain with phthalic ester identical, and asepsis environment-protecting, can replace phthalic ester plasticizer to be used for package plastics of food, medicine equipment and toy for children.At present BASF has started to produce in a large number Hexamoll DINCH product (DINCH is hexanaphthene-1, the abbreviation of 2-dioctyl phthalate dinonyl), and has obtained application on a lot of food product pack abroad and medicine equipment.Other non-toxic, environmental friendly softening agent also have citrate, vegetables oil, polymeric plasticizer etc.
Ethene-vinyl acetate-carbonyl (being called for short EVACO) is a kind of ethylene-dien terpolymer, the known softening agent that can be used as PVC.Compared with EVA, EVACO, owing to having introduced carbonyl in molecular structure, improves polarity, has promoted with PVC compatible.EVACO is migration and the extraction that can stop simple plasticizer as the maximum feature of flexible PVC properties-correcting agent, but its plasticizing efficiency is not as low molecule ester plasticizer.
Summary of the invention
In view of above-mentioned condition of the prior art, present inventor has carried out deeply and research widely at plasticized polyvinyl chloride Material Field, to finding a kind of nontoxic, transparent, processing temperature is suitable, mechanical property is excellent pvc material.Found that, to be selected from hexanaphthene-1,2-dioctyl phthalate di-isooctyl, hexanaphthene-1, one or more in these four kinds of softening agent of 2-dioctyl phthalate dinonyl, tributyl citrate and tributyl acetylcitrate as the co-plasticizer plasticized PVC that combines, can be realized aforementioned object as primary plasticizer and ethylene-vinyl acetate-carbonyl multipolymer.Ethylene-vinyl acetate-carbonyl multipolymer not only can further stop primary plasticizer from PVC, move and extract out, and PVC is also shown to toughening effect, makes not only can improve plastification but also can improve toughness and elasticity.The inventor has completed the present invention based on above-mentioned discovery just.
Therefore, an object of the present invention is to provide a kind of plasticized polyvinyl chloride material, this material non-toxic, the transparency is good, and processing temperature is suitable, excellent comprehensive mechanical property.
Another object of the present invention is to provide a kind of method of preparing plasticized polyvinyl chloride material of the present invention, can make easily material of the present invention by the method.
A further object of the present invention is to provide the purposes of plasticized polyvinyl chloride material of the present invention in food product pack and medicine equipment.
The technical scheme that realizes above-mentioned purpose of the present invention can be summarized as follows:
1, a plasticized polyvinyl chloride material, it comprises following component:
A) polyvinyl chloride resin of 100 weight parts;
B) one or more of 20-80 weight part are selected from the primary plasticizer of lower group: hexanaphthene-1,2-dioctyl phthalate di-isooctyl (DEHCH), hexanaphthene-1,2-dioctyl phthalate dinonyl (DINCH), tributyl citrate (TBC) and tributyl acetylcitrate (ATBC); And
C) 5-20 weight part is as ethylene-vinyl acetate-carbonyl multipolymer (EVACO) of co-plasticizer.
2, according to the plasticized polyvinyl chloride material described in the 1st, the mean polymerisation degree that wherein said polyvinyl chloride resin comprises 20-40 % by weight is 1000-1500, especially be that the PVC resin with low degree of polymerization of 1000-1300 and the mean polymerisation degree of 60-80 % by weight are 2000-2700, especially be the PVC with high of 2000-2500, more preferably the mean polymerisation degree that described polyvinyl chloride resin comprises 20-32 % by weight is 1000-1500, especially be that the PVC resin with low degree of polymerization of 1000-1300 and the mean polymerisation degree of 68-80 % by weight are 2000-2700, especially be the PVC with high of 2000-2500, based on the gross weight of described polyvinyl chloride resin.
According to the 1st or 2 described in plasticized polyvinyl chloride material, wherein by hexanaphthene-1,2-dioctyl phthalate di-isooctyl and/or hexanaphthene-1, the fluidizer of deciding for combination of 2-dioctyl phthalate dinonyl and tributyl citrate and/or tributyl acetylcitrate.
4. according to the plasticized polyvinyl chloride material described in any one in 1-3 item, wherein in ethylene-vinyl acetate-carbonyl multipolymer, the content of ethylene monomer unit is 58-70 % by weight, the content of vinyl acetate between to for plastic ester units is 20-32 % by weight, with the content of carbonyl unit be 7-15 % by weight, based on the gross weight of ethylene-vinyl acetate-carbonyl multipolymer; Preferably, in ethylene-vinyl acetate-carbonyl multipolymer, the content of ethylene monomer unit is 60-68 % by weight, and the content of vinyl acetate between to for plastic ester units is 23-30%, be generally 8-12 % by weight with the content of carbonyl unit, based on the gross weight of ethylene-vinyl acetate-carbonyl multipolymer; Particularly preferably use the Elvaloy741 type of du pont company and/or Elvaloy742 type resin as ethylene-vinyl acetate-carbonyl multipolymer.
5. according to the plasticized polyvinyl chloride material described in any one in 1-4 item, the ethylene-vinyl acetate-carbonyl multipolymer as co-plasticizer of the primary plasticizer that the polyvinyl chloride resin that wherein this material comprises based on every 100 weight parts comprises 30-70 weight part and 5-15 part.
6. according to the plasticized polyvinyl chloride material described in any one in 1-5 item, the polyvinyl chloride resin that wherein this material comprises based on every 100 weight parts, also comprises following component:
D) epoxy soybean oil of 1-10 weight part;
E) tricresyl phosphite of 0.1-1.0 weight part (nonyl phenyl ester);
F) polymethylphenyl siloxane fluid of 0.1-1.0 weight part; And
G) calcium-zinc composite stabilizing agent of 0.4-2.0 weight part.
7. according to the plasticized polyvinyl chloride material described in any one in 1-6 item, comprise following component:
A) polyvinyl chloride resin of 100 weight parts;
B) softening agent of 30-70 weight part;
C) ethylene-vinyl acetate-carbonyl multipolymer of 5-15 weight part;
D) epoxy soybean oil of 1-5 weight part;
E) tricresyl phosphite of 0.1-0.5 weight part (nonyl phenyl ester);
F) polymethylphenyl siloxane fluid of 0.1-0.5 weight part; And
G) calcium-zinc composite stabilizing agent of 0.7-1.5 weight part.
8. a method of preparing the plasticized polyvinyl chloride material as described in any one in 1-7 item, comprising:
1) polyvinyl chloride resin and other components except component C are mixed in high-speed mixer; And
2) by step 1) in obtain mixture transfer on double roll mill, add component C to carry out mixing, obtain plasticized polyvinyl chloride material.
9. according to the method described in the 8th, wherein step 1) in the temperature that is blended in 85-95 DEG C under carry out 15-20min; And/or step 2) in the mixing 15-20min that carries out at 155-165 DEG C.
10. the purposes in food product pack and medicine equipment according to the plasticized polyvinyl chloride material described in any one in 1-7, the especially purposes in food pack and film, tubing, infusion bag, blood transfusion tube, transfusion bags.
Embodiment
According to an aspect of the present invention, provide a kind of plasticized polyvinyl chloride material, it comprises following component:
A) polyvinyl chloride resin of 100 weight parts;
B) one or more of 20-80 weight part are selected from the primary plasticizer of lower group: hexanaphthene-1,2-dioctyl phthalate di-isooctyl (DEHCH), hexanaphthene-1,2-dioctyl phthalate dinonyl (DINCH), tributyl citrate (TBC) and tributyl acetylcitrate (ATBC); And
C) 5-20 weight part is as ethylene-vinyl acetate-carbonyl multipolymer of co-plasticizer.
In the present invention, PVC, as body material, has no particular limits for this material, and hard, flexible PVC all can use.
In a preferred embodiment of the invention, the mean polymerisation degree that comprises 20-40 % by weight as the polyvinyl chloride resin of component A is 1000-1500, especially be that the PVC resin with low degree of polymerization of 1000-1300 and the mean polymerisation degree of 60-80 % by weight are 2000-2700, especially be the PVC with high of 2000-2500, more preferably the mean polymerisation degree that comprises 20-32 % by weight as the polyvinyl chloride resin of component A is 1000-1500, especially be that the PVC resin with low degree of polymerization of 1000-1300 and the mean polymerisation degree of 68-80 % by weight are 2000-2700, especially be the PVC with high of 2000-2500, based on the gross weight of described polyvinyl chloride resin.In material of the present invention, PVC resin with low degree of polymerization can be improved the mobility of material in the course of processing, reduce processing temperature, and PVC with high can make the flexibility of material and elasticity be improved significantly.
In the present invention, adopt DEHCH, DINCH, TBC, wherein one or more of ATBC as the primary plasticizer of B component.These four kinds of softening agent are all non-toxic, environmental friendly softening agent, and polarity is larger, fine with PVC consistency.
Cyclohexane carboxylate class softening agent has more excellent low-temperature pliability and volatility resistance than citric acid ester plasticizer, but plasticizing efficiency and thermostability are slightly poorer than citric acid ester plasticizer, by this, two classes softening agent is composite adds in PVC, can obtain the plasticized polyvinyl chloride material that over-all properties is more excellent.Therefore, for the purpose of the present invention preferably, by the fluidizer of deciding for combination of DEHCH and/or DINCH and TBC and/or ATBC.
In plasticized polyvinyl chloride material of the present invention, the polyvinyl chloride resin of every 100 weight parts, the content of primary plasticizer is generally 20-80 weight part, preferably 30-70 weight part, particularly preferably 40-60 weight part.
In the present invention, adopt the use that combines with primary plasticizer as co-plasticizer of ethylene-vinyl acetate-carbonyl multipolymer.Secondary plasticizer used according to the invention is ethylene-vinyl acetate-carbonyl terpolymer (EVACO), and the chemical structure of this multipolymer is as follows:
EVACO is a kind of high molecular weight copolymer, toughness and elasticity that in the present invention not only can Reinforced PVC, and can as liquid plasticizer, easy migration not ooze out.EVACO can be by by carbon monoxide and ethene and vinyl acetate copolymerized acquisition.In EVACO, the content of ethylene monomer unit is generally 58-70 % by weight, and the content of vinyl acetate between to for plastic ester units is generally 20-32 % by weight, and the content of carbonyl unit is generally 7-15 % by weight, based on the gross weight of EVACO.Preferably, in EVACO, the content of ethylene monomer unit is generally 60-68 % by weight, and the content of vinyl acetate between to for plastic ester units is generally 23-30%, and the content of carbonyl unit is generally 8-12 % by weight, based on the gross weight of EVACO.
In a special embodiment of the present invention, as polymer modifiers ethylene-vinyl acetate-carbonyl multipolymer of component C, use Elvaloy741 type and/or Elvaloy742 resin from du pont company.
In plasticized polyvinyl chloride material of the present invention, the polyvinyl chloride resin of every 100 weight parts, the content of co-plasticizer EVACO is generally 5-20 weight part, preferably 5-15 weight part, particularly preferably 7-15 weight part.
In plasticized polyvinyl chloride material of the present invention, can also comprise other usual auxiliaries, for example other softening agent, lubricant, stablizer, antioxidant etc.
For example, in order to reduce costs, material of the present invention also can comprise 1-10 weight part by every 100 weight part PVC, preferably the epoxy soybean oil of 1-5 weight part.
Material of the present invention also can comprise 0.1-1.0 weight part by every 100 weight part PVC, and preferably 0.1-0.5 weight part tricresyl phosphite (nonyl phenyl ester) is as oxidation inhibitor and anti-aging agent.
Material of the present invention also can comprise 0.1-1.0 weight part by every 100 weight part PVC, and preferably 0.1-0.5 weight part polymethylphenyl siloxane fluid is as lubricant.
Material of the present invention also can comprise 0.4-2.0 weight part by every 100 weight part PVC, and preferably the calcium-zinc composite stabilizing agent of 0.7-1.5 weight part, is adding the degraded in man-hour to suppress PVC.Calcium-zinc composite stabilizing agent is the conventional stablizer of PVC materials hot working, and it can pass through one or more composite the obtaining in calcium stearate and Zinic stearas and polyvalent alcohol, phosphorous acid ester, beta-diketon, zeolite and hydrotalcite.For the present invention, all can use taking calcium stearate and Zinic stearas as the one package stabilizer of main component.
In a particularly preferred embodiment of the present invention, plasticized polyvinyl chloride material of the present invention comprises following component:
A) polyvinyl chloride resin of 100 weight parts;
B) softening agent of 30-70 weight part;
C) ethylene-vinyl acetate-carbonyl multipolymer of 5-15 weight part;
D) epoxy soybean oil of 1-5 weight part;
E) tricresyl phosphite of 0.1-0.5 weight part (nonyl phenyl ester);
F) polymethylphenyl siloxane fluid of 0.1-0.5 weight part; And
G) calcium-zinc composite stabilizing agent of 0.7-1.5 weight part.
In order to prepare plasticized polyvinyl chloride material of the present invention, the present invention also provides a kind of method of preparing it.
Therefore, according to a further aspect in the invention, provide a kind of method of preparing plasticized polyvinyl chloride material of the present invention, the method comprises:
1) polyvinyl chloride resin and other components except component C are mixed in high-speed mixer; And
2) by step 1) in obtain mixture transfer on double roll mill, add component C to carry out mixing, obtain plasticized polyvinyl chloride material.
Step 1) micromolecular additive and polyvinyl chloride resin are carried out pre-dispersed, can prevent that micromolecular additive from occurring to reunite and causing disperseing uneven in the time of twin-roll mixing.Because the polarity of component C is larger, by it separately in step 2) in add, can prevent that micromolecular additive from disperseing inhomogeneous because of the impact of component C.
Preferably, step 1) in the temperature that is blended in 85-95 DEG C under carry out 15-20min.Step 2) in the mixing 15-20min that carries out at 155-165 DEG C.
In preparation method's of the present invention step 1) in, advantageously, the temperature of high-speed mixer is 85-95 DEG C, mixing time is 15-20min, blade rotating speed 900-1100rpm.
In the step 2 of the inventive method) in, advantageously, the melting temperature of double roll mill is 155-165 DEG C, mixing time is 15-20min, roller spacing 1-3mm, roller rotating speed 40-55rpm.
Plasticized polyvinyl chloride material of the present invention has the following advantages: adopted non-toxic, environmental friendly softening agent, can be used for the field such as food product pack and medical device, human body is safe from harm.Selected softening agent polarity is larger, good with the consistency of PVC, be uniformly dispersed, and be in use difficult for moving out from material internal, and the processing temperature that makes material has been reduced to 160 DEG C, than the PVC material of the phthalic ester plasticising such as DEHP, it has more excellent low-temperature pliability, tensile strength and elongation at break etc., and adds the softening agent of small amount just can reach good performance requriements.In addition, the EVACO type modifier adding in material of the present invention, is a kind of high-molecular copolymer, toughness and elasticity that can Reinforced PVC, and can as liquid plasticizer, not produce migration, be a kind of permanent softening agent, and interception is played in migration and extraction to primary plasticizer.In the time that polyvinyl chloride resin of the present invention adopts the mixture of high-polymerization degree resin and oligomeric resin and high-polymerization degree resin as body material, flexibility, elasticity and the intensity of gained plastification material all obvious more conventional pvc material (polymerization degree is at 1050-1100) is good, particularly low-temperature performance.Plasticized polyvinyl chloride of the present invention also has the excellent transparency, and being specially adapted to some has the goods of requirement to the transparency.
Therefore, plasticized polyvinyl chloride material of the present invention is particularly suitable for the field such as food product pack and medical device.
Therefore, according to last aspect of the present invention, provide plasticized polyvinyl chloride material spy of the present invention purposes in food product pack and medical device, especially the purposes in food pack and film, tubing, infusion bag, blood transfusion tube, transfusion bags.
Embodiment
In each of the embodiments described below, if do not specify, what each component concentration adopted is parts by weight.
In following embodiment, adopt following methods to test gained plasticized polyvinyl chloride material:
Ballistic method embrittlement temperature: GB/T5470-2008
Shock strength: GB/T1843-2008, test at-30 DEG C.
Tensile property: GB/T528-1992
Hardness: GB/T531-1999
Volatility: ASTMD1023-94 (2003)
Embodiment 1
The PVC resin with low degree of polymerization that is 1050 by 25 parts of mean polymerisation degree, the PVC with high that 75 parts of polymerization degree are 2400 and the calcium-zinc composite stabilizing agent (from the 106-8 type of Shanghai Yong Yan Chemical Industry Science Co., Ltd) of 1.2 parts first add high-speed mixer, start stirring, blade rotating speed is 950rpm, temperature rises to 90 DEG C, keep rotating speed and temperature, add successively the DEHCH softening agent of 45 parts, the epoxy soybean oil of 5 parts, the tricresyl phosphite (nonyl phenyl ester) of 0.4 part and the polymethylphenyl siloxane fluid of 0.3 part, be uniformly mixed after 15min, mixture is transferred in double roll mill and carried out mixing with the Elvaloy741 of 10 parts, melting temperature is controlled at 165 DEG C, roller spacing is 2min, roller rotating speed is 55rpm, mixing time is 15min, then the mixing blend obtaining through and being extruded again, granulation, injection is made sample and is tested.
Each test result is in table 1 and table 2.
Embodiment 2
Repeat embodiment 1, difference is: the PVC resin with low degree of polymerization that is 1050 by mean polymerisation degree makes 37 parts into, and the PVC with high that mean polymerisation degree is 2400 makes 63 parts into.
Each test result is in table 1 and table 2.
Embodiment 3
Repeat embodiment 1, difference is: the PVC that high DP PVC is replaced with to mean polymerisation degree 2100.
Each test result is in table 1 and table 2.
Embodiment 4
Repeat embodiment 1, difference is: change the umber of Elvaloy741 into 18 parts.
Each test result is in table 1 and table 2.
Comparative example 5
Repeat embodiment 1, difference is: do not add Elvaloy741.
Each test result is in table 1 and table 2.
Embodiment 6
Repeat embodiment 1, difference is: the plastic binder that the DEHCH softening agent of 45 parts is changed into 20 parts of DEHCH and 25 parts of ATBC.
Each test result is in table 1 and table 2.
Embodiment 7
Repeat embodiment 1, difference is: change the add-on of DEHCH into 70 parts.
Each test result is in table 1 and table 2.
Embodiment 8
Repeat embodiment 1, difference is: change the DEHCH of 45 parts into the DEHCH of 15 parts and the ATBC of 15 parts.
Each test result is in table 1 and table 2.
Embodiment 9
Repeat embodiment 1, difference is: it is 1450 PVC that PVC resin with low degree of polymerization is replaced with to mean polymerisation degree.
Each test result is in table 1 and table 2.
Embodiment 10
Repeat embodiment 1, difference is: change the DEHCH softening agent of 45 parts into the DINCH of 20 parts and the TBC of 25 parts.
Each test result is in table 1 and table 2.
Embodiment 11
Repeat embodiment 1, difference is: change the umber of Elvaloy741 into 6 parts.
Each test result is in table 1 and table 2.
Embodiment 12
Repeat embodiment 1, difference is: the DEHCH softening agent of 45 parts is changed into the ATBC softening agent of 45 parts.
Each test result is in table 1 and table 2.
Embodiment 13
Repeat embodiment 1, difference is: it is 1100 polyvinyl chloride resin that the polyvinyl chloride resin of 100 parts all adopts mean polymerisation degree.
Each test result is in table 1 and table 2.
Embodiment 14
Repeat embodiment 1, difference is: it is 2400 polyvinyl chloride resin that the polyvinyl chloride resin of 100 parts all adopts mean polymerisation degree.
Each test result is in table 1 and table 2.
Comparative example 15
Repeat embodiment 12, difference is: do not add Elvaloy741.
Each test result is in table 1 and table 2.
Embodiment 16
Repeat embodiment 1, difference is: do not add epoxy soybean oil, tricresyl phosphite (nonyl phenyl ester) and polymethylphenyl siloxane fluid.
Each test result is in table 1 and table 2.
Table 1
Table 2
Claims (10)
1. a plasticized polyvinyl chloride material, it comprises following component:
A) polyvinyl chloride resin of 100 weight parts;
B) one or more of 20-80 weight part are selected from the primary plasticizer of lower group: hexanaphthene-1,2-dioctyl phthalate di-isooctyl (DEHCH), hexanaphthene-1,2-dioctyl phthalate dinonyl (DINCH), tributyl citrate (TBC) and tributyl acetylcitrate (ATBC); And
C) 5-20 weight part is as ethylene-vinyl acetate-carbonyl multipolymer (EVACO) of co-plasticizer.
2. plasticized polyvinyl chloride material according to claim 1, the mean polymerisation degree that wherein said polyvinyl chloride resin comprises 20-40 % by weight is 1000-1500, especially be that the PVC resin with low degree of polymerization of 1000-1300 and the mean polymerisation degree of 60-80 % by weight are 2000-2700, especially be the PVC with high of 2000-2500, more preferably the mean polymerisation degree that described polyvinyl chloride resin comprises 20-32 % by weight is 1000-1500, especially be that the PVC resin with low degree of polymerization of 1000-1300 and the mean polymerisation degree of 68-80 % by weight are 2000-2700, especially be the PVC with high of 2000-2500, based on the gross weight of described polyvinyl chloride resin.
3. plasticized polyvinyl chloride material according to claim 1 and 2, wherein by hexanaphthene-1,2-dioctyl phthalate di-isooctyl and/or hexanaphthene-1, the fluidizer of deciding for combination of 2-dioctyl phthalate dinonyl and tributyl citrate and/or tributyl acetylcitrate.
4. according to the plasticized polyvinyl chloride material described in any one in claim 1-3, wherein in ethylene-vinyl acetate-carbonyl multipolymer, the content of ethylene monomer unit is 58-70 % by weight, the content of vinyl acetate between to for plastic ester units is 20-32 % by weight, with the content of carbonyl unit be 7-15 % by weight, based on the gross weight of ethylene-vinyl acetate-carbonyl multipolymer; Preferably, in ethylene-vinyl acetate-carbonyl multipolymer, the content of ethylene monomer unit is 60-68 % by weight, and the content of vinyl acetate between to for plastic ester units is 23-30%, be generally 8-12 % by weight with the content of carbonyl unit, based on the gross weight of ethylene-vinyl acetate-carbonyl multipolymer; Particularly preferably use the Elvaloy741 type of du pont company and/or Elvaloy742 type resin as ethylene-vinyl acetate-carbonyl multipolymer.
5. according to the plasticized polyvinyl chloride material described in any one in claim 1-4, the ethylene-vinyl acetate-carbonyl multipolymer as co-plasticizer of the primary plasticizer that the polyvinyl chloride resin that wherein this material comprises based on every 100 weight parts comprises 30-70 weight part and 5-15 part.
6. according to the plasticized polyvinyl chloride material described in any one in claim 1-5, the polyvinyl chloride resin that wherein this material comprises based on every 100 weight parts, also comprises following component:
D) epoxy soybean oil of 1-10 weight part;
E) tricresyl phosphite of 0.1-1.0 weight part (nonyl phenyl ester);
F) polymethylphenyl siloxane fluid of 0.1-1.0 weight part; And
G) calcium-zinc composite stabilizing agent of 0.4-2.0 weight part.
7. according to the plasticized polyvinyl chloride material described in any one in claim 1-6, comprise following component:
A) polyvinyl chloride resin of 100 weight parts;
B) softening agent of 30-70 weight part;
C) ethylene-vinyl acetate-carbonyl multipolymer of 5-15 weight part;
D) epoxy soybean oil of 1-5 weight part;
E) tricresyl phosphite of 0.1-0.5 weight part (nonyl phenyl ester);
F) polymethylphenyl siloxane fluid of 0.1-0.5 weight part; And
G) calcium-zinc composite stabilizing agent of 0.7-1.5 weight part.
8. a method of preparing the plasticized polyvinyl chloride material as described in any one in claim 1-7, comprising:
1) polyvinyl chloride resin and other components except component C are mixed in high-speed mixer; And
2) by step 1) in obtain mixture transfer on double roll mill, add component C to carry out mixing, obtain plasticized polyvinyl chloride material.
9. method according to claim 8, wherein step 1) in the temperature that is blended in 85-95 DEG C under carry out 15-20min; And/or step 2) in the mixing 15-20min that carries out at 155-165 DEG C.
10. the purposes in food product pack and medicine equipment according to the plasticized polyvinyl chloride material described in any one in claim 1-7, the especially purposes in food pack and film, tubing, infusion bag, blood transfusion tube, transfusion bags.
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| CN104448613A (en) * | 2014-11-27 | 2015-03-25 | 中广核三角洲（江苏）塑化有限公司 | Environment-friendly, low-volatility and low-odor PVC (polyvinyl chloride) cable material and preparation method thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100999601A (en) * | 2006-12-26 | 2007-07-18 | 上海新上化高分子材料有限公司 | Medical polyvinyl chloride plastic and preparation process thereof |
| CN101152582A (en) * | 2006-09-30 | 2008-04-02 | 山东威高集团医用高分子制品股份有限公司 | Thin-film material for medical purpose |
| CN101215398A (en) * | 2007-12-28 | 2008-07-09 | 上海新上化高分子材料有限公司 | Non-ortho-benzene medical soft polyvinyl chloride plastic and preparation method thereof |
| CN101434732A (en) * | 2008-12-24 | 2009-05-20 | 佛山市顺德区金康业塑料有限公司 | Medical soft polychloroethylene plastic without o-benzene series plasticiser |
| CN102875921A (en) * | 2012-10-12 | 2013-01-16 | 南京工业大学 | Food grade plasticizing polrvinyl chloride (PVC) glove and preparation method thereof |
-
2013
- 2013-01-25 CN CN201310030898.2A patent/CN103965564B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101152582A (en) * | 2006-09-30 | 2008-04-02 | 山东威高集团医用高分子制品股份有限公司 | Thin-film material for medical purpose |
| CN100999601A (en) * | 2006-12-26 | 2007-07-18 | 上海新上化高分子材料有限公司 | Medical polyvinyl chloride plastic and preparation process thereof |
| CN101215398A (en) * | 2007-12-28 | 2008-07-09 | 上海新上化高分子材料有限公司 | Non-ortho-benzene medical soft polyvinyl chloride plastic and preparation method thereof |
| CN101434732A (en) * | 2008-12-24 | 2009-05-20 | 佛山市顺德区金康业塑料有限公司 | Medical soft polychloroethylene plastic without o-benzene series plasticiser |
| CN102875921A (en) * | 2012-10-12 | 2013-01-16 | 南京工业大学 | Food grade plasticizing polrvinyl chloride (PVC) glove and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 吴加琦: ""介绍美国杜邦公司的突破性聚氯乙烯树脂永久改性剂"", 《聚氯乙烯》 * |
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