CN113024970A - High-environment-friendly odorless transparent medical sizing material and preparation method thereof - Google Patents

High-environment-friendly odorless transparent medical sizing material and preparation method thereof Download PDF

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CN113024970A
CN113024970A CN202110267930.3A CN202110267930A CN113024970A CN 113024970 A CN113024970 A CN 113024970A CN 202110267930 A CN202110267930 A CN 202110267930A CN 113024970 A CN113024970 A CN 113024970A
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parts
environment
transparent medical
odorless
type powder
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李朋
陈朝辆
李�浩
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Dongguan Liteng Plastic Technology Co ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/10Esters; Ether-esters
    • C08K5/11Esters; Ether-esters of acyclic polycarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/06Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/34Silicon-containing compounds
    • C08K3/36Silica
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/04Ingredients treated with organic substances
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/08Ingredients agglomerated by treatment with a binding agent
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/10Transparent films; Clear coatings; Transparent materials

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The application relates to the technical field of medical materials, in particular to a high-environment-friendly odorless transparent medical sizing material and a preparation method thereof. The high-environment-friendly odorless transparent medical sizing material is mainly prepared from the following components in parts by weight: 80-120 parts of five-type powder; 45-70 parts of citric acid ester; 1-3 parts of calcium-zinc environment-friendly heat stabilizer; 0.1-0.5 part of liquid lubricant; the preparation method comprises the following steps: kneading the five-type powder, the citric acid ester, the calcium-zinc environment-friendly heat stabilizer and the liquid lubricant according to the weight part ratio, and extruding, granulating and molding after the materials are uniformly mixed and sufficiently kneaded to obtain the high-environment-friendly odorless transparent medical sizing material. The high-environment-friendly odorless transparent medical sizing material can be used for manufacturing transparent medical infusion tubes, catheters and the like and transparent soles, and has the advantages of being odorless, good in extraction resistance and non-toxic.

Description

High-environment-friendly odorless transparent medical sizing material and preparation method thereof
Technical Field
The application relates to the technical field of medical materials, in particular to a high-environment-friendly odorless transparent medical sizing material and a preparation method thereof.
Background
With the increasing supervision of the clinical application on the use performance and safety performance of medical instruments and medical materials, the influence of the medical materials on the safety and health of human bodies is receiving increasing attention. Among them, the most commonly used medical catheters are used for connecting tubular products inside and outside the human body, and are widely used as passages for drainage, perfusion, administration, blood collection, blood transfer, detection of biological conditions by a sensor, and auxiliary introduction of other medical instruments. Medical catheters have become an indispensable tool in clinical medicine.
The current medical catheter is generally made of PVC material, because the PVC material has the advantages of chemical corrosion resistance, good low permeability of gas and water vapor, good comprehensive mechanical property, good transparency of products and the like, and meanwhile, the PVC material is also a universal material with the most excellent cost performance.
In related PVC medical sizing materials, a plasticizer DEHP is used as a plasticizer in a PVC medical sizing material formula, and the prepared PVC medical sizing material can cause potential safety hazards to a human body in clinical application, because the plasticizer DEHP migrates and enters the human body along with components of transfusion and blood transfusion, so that toxic and side effects such as liver carcinogenesis, female fertility reduction, growth and development retardation of infants and children, damage to peripheral nervous systems and the like are caused, namely the problems of low environmental protection safety and easiness in release of toxic and harmful substances exist.
Disclosure of Invention
The application provides a high-environment-friendly odorless transparent medical sizing material and a preparation method thereof, and the sizing material has the advantages of being odorless, good in extraction resistance, non-toxic and the like.
In a first aspect, the application provides a high-environment-friendly odorless transparent medical rubber material, which adopts the following technical scheme:
a high-environment-friendly odorless transparent medical sizing material is mainly prepared from the following components in parts by weight:
80-120 parts of five-type powder;
45-70 parts of a plasticizer;
1-3 parts of calcium-zinc environment-friendly heat stabilizer;
0.1-0.5 part of liquid lubricant;
wherein the plasticizer is citrate.
Through adopting above-mentioned technical scheme, adopt citrate to use as the plasticizer, because citrate's toxicity is very low, get into easily in the human body and be decomposed, absorb and excrete, easily biodegradable after discharging to the external environment, this application adopts citrate to replace plasticizer DEHP completely, and does not have other poisonous and harmful substances of addition in the prescription, therefore the high environmental protection tasteless transparent sizing material for medical treatment that this application prepared has nontoxic, the resistant good and tasteless advantage of taking out.
Preferably, the five-type powder is modified five-type powder, and the modified five-type powder mainly comprises the following preparation steps:
mixing 20-30 parts of five-type powder and 0.1-0.3 part of fumed silica, continuously stirring, firstly heating to 100-120 ℃ for 30min, then cooling to 45-60 ℃ for 15min, and obtaining the modified five-type powder.
By adopting the technical scheme, the five-type powder is modified by the method and then is used for preparing the high-environment-friendly odorless transparent medical sizing material, the extraction resistance of the sizing material can be improved, and the reason may be that: the particle size of the gas-phase method silicon dioxide is small, so that the gas-phase method silicon dioxide can be well dispersed in a system, a temporary three-dimensional network structure is formed through the hydrogen bond action between silicon hydroxyl groups on the surface of molecules, the migration difficulty of each component in the system is enhanced, the stability of each component in the system is enhanced, and the gas-phase method silicon dioxide is non-toxic and odorless, so that the extraction resistance of the environment-friendly odorless transparent medical sizing material can be improved on the basis of keeping the non-toxic and odorless properties of the environment-friendly odorless transparent medical sizing material.
Preferably, the rotation speed for starting the mixing and stirring is 2500r/min, and then the temperature is raised under the rotation speed of 750r/min adjusted to 500-.
By adopting the technical scheme, the stirring speed is controlled within 2500r/min at first, the five-type powder and the gas phase method silicon dioxide can be fully mixed in advance, and then the stirring speed is controlled within 750r/min at second, so that the five-type powder and the gas phase method silicon dioxide can fully act.
Preferably, the fumed silica is pretreated, and the pretreatment mainly comprises the following steps:
the method comprises the following steps: slowly adding 8-20 parts of polyvinyl alcohol into 10-15 parts of fumed silica, stirring and mixing, then adding 5-8 parts of absolute ethyl alcohol, and then distilling at 80-85 ℃ to make the material viscous;
step two: and (3) dropwise adding 0.05-0.1 part of aluminate coupling agent into the material obtained in the step one, reacting for 1-2h, drying and grinding.
By adopting the technical scheme, the five-type powder is modified by adopting the fumed silica to prepare the high-environment-friendly odorless transparent medical sizing material, so that the plastic deformation capacity of the high-environment-friendly odorless transparent medical sizing material is reduced, and the tensile strength of the high-environment-friendly odorless transparent medical sizing material can be improved after the fumed silica is treated by the method.
Preferably, the aluminate coupling agent is aluminate coupling agent DL-411.
By adopting the technical scheme, the aluminate coupling agent DL-411 is light in color, nontoxic and tasteless, is suitable for preparing the high-environment-friendly tasteless transparent medical sizing material, has good synergistic thermal stability and lubricity on PVC, and can improve the extraction resistance of the high-environment-friendly tasteless transparent medical sizing material, and in addition, the tensile strength of the high-environment-friendly tasteless transparent medical sizing material can be further improved by adopting the specific aluminate coupling agent DL-411.
Preferably, the modified five-type powder is 80-100 parts, and the citrate is 60-70 parts.
By adopting the technical scheme and the modified five-type powder and the citric acid ester in the specific ratio, the prepared high-environment-friendly odorless transparent medical rubber material is further improved in the extraction resistance.
Preferably, the high-environment-friendly odorless transparent medical rubber material is mainly prepared from the following components in parts by weight:
100 parts of modified five-type powder;
60 parts of citric acid ester;
1.6 parts of calcium-zinc environment-friendly heat stabilizer;
0.3 part of liquid lubricant.
By adopting the technical scheme and the specific proportioning scheme, the prepared high-environment-friendly odorless transparent medical sizing material has better extraction resistance.
In a second aspect, the application provides a preparation method of a high-environment-friendly odorless transparent medical rubber material, which adopts the following technical scheme:
a preparation method of a high-environment-friendly odorless transparent medical rubber material comprises the following steps: kneading the five-type powder, the citric acid ester, the calcium-zinc environment-friendly heat stabilizer and the liquid lubricant according to the weight part ratio, and extruding, granulating and molding after the materials are uniformly mixed and sufficiently kneaded to obtain the high-environment-friendly odorless transparent medical sizing material.
By adopting the technical scheme, the high-environment-friendly odorless transparent medical sizing material can be obtained by fully kneading the components and then extruding and granulating, and the preparation method is simple and easy to operate.
Preferably, the kneading rotation speed is 1000-. The extrusion temperature is 110-130 ℃.
By adopting the technical scheme, the kneading rotating speed and the extruding temperature are correspondingly controlled within the ranges, so that the components can be fully acted, and the structural performance of the components is not easy to damage.
In summary, the present application has the following beneficial effects:
1. because this application adopts citrate as plasticizer, because citrate's toxicity is very low, easily be decomposed in getting into the human body, absorb and excrete, easily biodegradable after discharging to the external environment, therefore the high environmental protection tasteless transparent sizing material for medical treatment that this application was prepared has nontoxic, resistant drawability is good and tasteless advantage.
2. In the application, the fumed silica is preferably adopted to modify the five-type powder, so that the extraction resistance of the environment-friendly odorless transparent medical sizing material can be improved on the basis of keeping the nontoxic and odorless performance of the environment-friendly odorless transparent medical sizing material.
3. By selecting the specific aluminate coupling agent DL-411, the drawing resistance of the high-environment-friendly odorless transparent medical sizing material can be improved, and the tensile strength of the high-environment-friendly odorless transparent medical sizing material can be further improved.
Detailed Description
The present application will be described in further detail with reference to examples.
The sources of the raw materials involved in the following preparations, examples and comparative examples are as follows:
table 1 raw material source table
Figure BDA0002973002680000041
Preparation example 1
The modified five-type powder comprises the following specific preparation steps:
at the rotating speed of 2000r/min, 20 parts of five-type powder and 0.1 part of pretreated fumed silica are mixed, then the rotating speed is adjusted to 750r/min, the temperature is firstly increased to 100 ℃ and kept for 30min, and then the mixture is cooled to 45 ℃ and kept for 15min, so that the modified five-type powder is obtained.
Preparation example 2
The modified five-type powder comprises the following specific preparation steps:
pretreatment of silicon dioxide by a gas phase method:
the method comprises the following steps: slowly adding 8 parts of polyvinyl alcohol into 10 parts of fumed silica, stirring and mixing, then adding 5 parts of absolute ethyl alcohol, and then distilling at 80 ℃ to enable the material to be viscous;
step two: and (3) dropwise adding 0.05 part of aluminate coupling agent into the material obtained in the step one, reacting for 1h by using the aluminate coupling agent UP-802, drying and grinding.
Modifying five types of powder:
mixing 30 parts of five-type powder and 0.3 part of pretreated fumed silica at the rotating speed of 2500r/min, then adjusting the rotating speed to 500r/min, firstly heating to 120 ℃ and keeping for 30min, and then cooling to 60 ℃ and keeping for 15min to obtain the modified five-type powder.
Preparation example 3
The modified five-type powder comprises the following specific preparation steps:
pretreatment of silicon dioxide by a gas phase method:
the method comprises the following steps: slowly adding 20 parts of polyvinyl alcohol into 15 parts of fumed silica, stirring and mixing, then adding 8 parts of absolute ethyl alcohol, and then distilling at 85 ℃ to enable the material to be viscous;
step two: and (3) dropwise adding 0.05 part of aluminate coupling agent into the material obtained in the step one, reacting for 2 hours by using the aluminate coupling agent UP-802, drying and grinding.
Modifying five types of powder:
at the rotating speed of 2000r/min, 20 parts of five-type powder and 0.1 part of pretreated fumed silica are mixed, then the rotating speed is adjusted to 750r/min, the temperature is firstly increased to 100 ℃ and kept for 30min, and then the mixture is cooled to 45 ℃ and kept for 15min, so that the modified five-type powder is obtained.
Preparation example 4
A modified penta-powder is different from the preparation example 3 in that an aluminate coupling agent DL-411 is adopted to replace an aluminate coupling agent UP-802 in the pretreatment step of gas-phase method silicon dioxide.
Example 1
A high-environment-friendly odorless transparent medical rubber material is prepared by the following steps: and (2) at the rotating speed of 1000rpm/min, adding 80g of five-type powder, 70g of citric acid ester, 1g of calcium-zinc environment-friendly heat stabilizer and 0.1g of liquid lubricant into a high-speed stirring cylinder for kneading, and after the materials are uniformly mixed and sufficiently kneaded, extruding, granulating and molding at 110 ℃ to obtain the high-environment-friendly odorless transparent medical rubber material.
Example 2
A high-environment-friendly odorless transparent medical rubber material is prepared by the following steps: and (2) at the rotating speed of 1300rpm/min, adding 120g of five-type powder, 45g of citric acid ester, 3g of calcium-zinc environment-friendly heat stabilizer and 0.5g of liquid lubricant into a high-speed stirring cylinder for kneading, and after the materials are uniformly mixed and sufficiently kneaded, extruding, granulating and molding at 130 ℃ to obtain the high-environment-friendly odorless transparent medical rubber material.
Example 3
A high-environment-friendly odorless transparent medical rubber material is prepared by the following steps: 100g of five-type powder, 60g of citrate, 1.6g of calcium-zinc environment-friendly heat stabilizer and 0.3g of liquid lubricant are put into a high-speed stirring cylinder at the rotating speed of 1200rpm/min for kneading, and after the materials are uniformly mixed and sufficiently kneaded, the materials are extruded and granulated at 120 ℃ for forming, so that the high-environment-friendly odorless transparent medical rubber material is obtained.
Example 4
A high-environment-friendly odorless transparent medical rubber material is different from the rubber material in example 1 in that the modified five-type powder prepared in preparation example 1 is used for replacing five-type powder.
Example 5
A high-environment-friendly odorless transparent medical rubber material is different from that of example 1 in that the modified five-type powder prepared in preparation example 2 is used instead of the five-type powder.
Example 6
A high-environment-friendly odorless transparent medical rubber material is different from that of example 2 in that the modified five-type powder prepared in preparation example 3 is used instead of the five-type powder.
Example 7
A highly environmentally friendly odorless transparent medical rubber material is different from that of example 6 in that the modified V-shaped powder prepared in preparation example 4 is used.
Comparative example 1
A highly environmentally friendly, odorless, transparent medical gum material differing from example 3 in that the plasticizer DEHP was used instead of citrate as the plasticizer of the formulation.
TABLE 2 composition ratio table for each example and each ratio
Figure BDA0002973002680000061
Performance testing test transparency test: the transparency test was carried out according to GBT2410-2008 for examples 1-7 and comparative example 1, and the test results are shown in Table 3.
And (3) testing tensile strength: tensile strength tests were carried out according to GB1040-79 on examples 1-7 and comparative example 1, and the test results are shown in Table 3.
And (3) testing extraction resistance: the high environmental protection, odorless, transparent medical rubber compound prepared in each example and comparative example was formed into a strip, and each strip was immersed in an n-heptane solution and extracted at 36.5 ℃ for 1 hour. After extraction, 300ml of the n-heptane solution after the test was taken, concentrated using a rotary evaporator, transferred to an evaporation dish and evaporated to dryness at 105 ℃ for 2 hours. The weight of the evaporation residue at this time was measured to determine the content of the evaporation residue in 300ml of n-heptane, and the content of the evaporation residue ≦ 30ppm was determined as an acceptable value, and the specific measurement results are shown in Table 3.
TABLE 3 test results for each example and each comparative example
Item Degree of transparency% Tensile strength, MPa Solvent extraction, ppm
Example 1 96 83 22
Example 2 98 87 29
Example 3 98 85 16
Example 4 97 73 10
Example 5 98 82 10
Example 6 97 85 11
Example 7 96 98 6
Comparative example 1 96 86 1089
As can be seen from examples 1 to 7 in combination with Table 3, the high-environmental-protection odorless transparent medical rubber compound prepared by using citric acid ester as a plasticizer has the advantages that the transparency can reach more than 95%, the content of residues in the detection of solvent extraction is below 30ppm, and the prepared high-environmental-protection odorless transparent medical rubber compound is nontoxic and odorless and has good extraction resistance because all components in the formula are low-toxicity and odorless substances.
As can be seen from the combination of examples 1 and 2 and Table 3, the compounding ratio of example 1 was used to reduce the residue content from 29ppm to 16ppm in the solvent extraction test, and it was found that the extraction resistance of the transparent medical rubber composition of example 1 was improved.
As can be seen from the combination of examples 2 and 3 and Table 3, the compounding ratio of example 3 was used to further reduce the residue content from 16ppm to 10ppm in the solvent extraction test, so that it was found that the extraction resistance of the high-environmental-friendly odorless transparent medical rubber was further improved by the compounding ratio of example 3.
It can be seen from the combination of examples 1 and 4 and table 3 that the extraction resistance of the highly environmentally friendly odorless transparent medical rubber compound prepared from the five-type powder modified by fumed silica can be significantly improved.
It can be seen from the combination of examples 4 and 5, examples 2 and 6 and table 3 that the high-environmental-protection odorless transparent medical sizing material prepared by further performing surface treatment on fumed silica on the basis of the five-type powder modified by fumed silica can solve the problem that the plastic deformation effect of the product is reduced due to modification of fumed silica, namely the tensile strength of the product is improved, and meanwhile, the good extraction resistance of the product can be maintained.
As can be seen from the combination of examples 6 to 7 and Table 3, the use of the specific aluminate coupling agent DL-411 in the surface treatment of fumed silica not only further improves the tensile strength but also the draw-out resistance of the highly environmentally friendly, odorless, transparent medical rubber compound.
By combining example 3 and comparative example 1 and table 3, it can be seen that the use of citric acid ester instead of DEHP as a plasticizer in the formulation can improve the problem of harmful substances that are toxic and harmful to human health, and obtain a high-environmental-protection odorless transparent medical sizing material with no toxicity, no odor and excellent extraction resistance.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.

Claims (10)

1. The high-environment-friendly odorless transparent medical rubber material is characterized by being mainly prepared from the following components in parts by weight:
80-120 parts of five-type powder;
45-70 parts of a plasticizer;
1-3 parts of calcium-zinc environment-friendly heat stabilizer;
0.1-0.5 part of liquid lubricant;
wherein the plasticizer is citrate.
2. The high environmental protection, odorless and transparent medical compound according to claim 1, wherein: the five-type powder is modified five-type powder, and the modified five-type powder mainly comprises the following preparation steps:
mixing 20-30 parts of five-type powder and 0.1-0.3 part of fumed silica, continuously stirring, firstly heating to 100-120 ℃ for 30min, then cooling to 45-60 ℃ for 15min, and obtaining the modified five-type powder.
3. A highly environmentally friendly, odorless, transparent medical compound according to claim 2, wherein: the rotation speed for starting the mixing and stirring is 2000-2500r/min, and then the rotation speed is adjusted to be 500-750r/min, and then the temperature is raised.
4. A high environmental protection, odorless and transparent medical compound according to claim 2 or 3, wherein: the fumed silica is pretreated, and the pretreatment mainly comprises the following steps:
the method comprises the following steps: slowly adding 8-20 parts of polyvinyl alcohol into 10-15 parts of fumed silica, stirring and mixing, then adding 5-8 parts of absolute ethyl alcohol, and then distilling at 80-85 ℃ to make the material viscous;
step two: and (3) dropwise adding 0.05-0.1 part of aluminate coupling agent into the material obtained in the step one, reacting for 1-2h, drying and grinding.
5. The high environmental protection, odorless and transparent medical compound according to claim 4, wherein: the aluminate coupling agent is an aluminate coupling agent DL-411.
6. A high environmental protection, odorless and transparent medical compound according to any one of claims 2 to 3 and 5, wherein: 80-100 parts of modified five-type powder and 60-70 parts of citric acid ester.
7. A high environmental protection, odorless and transparent medical compound according to any one of claims 2 to 3 and 5, wherein: the paint is mainly prepared from the following components in parts by weight:
100 parts of modified five-type powder;
60 parts of citric acid ester;
1.6 parts of calcium-zinc environment-friendly heat stabilizer;
0.3 part of liquid lubricant.
8. A process for preparing a transparent medical composition having a high environmental protection and a low odor as claimed in any one of claims 1 to 7, comprising the steps of: kneading the five-type powder, the citric acid ester, the calcium-zinc environment-friendly heat stabilizer and the liquid lubricant according to the weight part ratio, and extruding, granulating and molding after the materials are uniformly mixed and sufficiently kneaded to obtain the high-environment-friendly odorless transparent medical sizing material.
9. The method for preparing a high-environmental-protection odorless transparent medical rubber compound according to claim 8, wherein the method comprises the following steps: the kneading speed is 1000-1300 rpm/min.
10. A process for preparing a transparent medical composition having high environmental protection and no odor according to claim 8 or 9, wherein: the extrusion temperature is 110-130 ℃.
CN202110267930.3A 2021-03-11 2021-03-11 High-environment-friendly odorless transparent medical sizing material and preparation method thereof Pending CN113024970A (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102504437A (en) * 2011-10-19 2012-06-20 江南大学 Preparation method of environmentally-friendly disposable polyvinyl chloride glove

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102504437A (en) * 2011-10-19 2012-06-20 江南大学 Preparation method of environmentally-friendly disposable polyvinyl chloride glove

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
张俊甫: "《精细化工概论》", 31 October 1991, 中央广播电视大学出版社, pages: 113 *
杨宝红等: "纳米无机粒子抑制喷绘PVC膜中增塑剂析出的研究", 《中国塑料》 *
杨宝红等: "纳米无机粒子抑制喷绘PVC膜中增塑剂析出的研究", 《中国塑料》, vol. 24, no. 2, 28 February 2010 (2010-02-28), pages 83 - 86 *
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