CN109535685B - Calcium magnesium zinc liquid stabilizer and application thereof - Google Patents
Calcium magnesium zinc liquid stabilizer and application thereof Download PDFInfo
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Abstract
The invention discloses a calcium-magnesium-zinc liquid stabilizer and application thereof. At present, the problems of water mist whitening, bag adhesion and the like can occur after the common PVC material is sterilized by high-temperature and high-pressure steam. The calcium-magnesium-zinc liquid stabilizer comprises zinc salt of organic acid, calcium oleate, magnesium salt of organic acid, segmented polyethylene oxide-polypropylene oxide ricinoleate with molecular weight of 2400-2600 and a solvent; the block polyethylene oxide-polypropylene oxide ricinoleate has the molar ratio of EO to PO of 1: 3-4. The calcium-magnesium-zinc liquid stabilizer has the advantages of good synergistic performance of all components, good compatibility with polyvinyl chloride resin, no toxicity and environmental protection. The calcium-magnesium-zinc liquid stabilizer has excellent transparency, high temperature adhesion resistance and water mist whitening resistance on soft PVC, and has an outstanding solving effect on the problems of the existing blood transfusion (liquid) instruments in practical application.
Description
Technical Field
The invention relates to a polyvinyl chloride heat stabilizer, in particular to a calcium magnesium zinc liquid stabilizer and application thereof.
Background
The application of polyvinyl chloride (PVC) resin is very important in the field of medical blood (fluid) transfusion instruments. The medical blood (fluid) transfusion container film is generally manufactured by rolling soft PVC material, and then is made into a bag by high-frequency heat synthesis, and a whole set of blood (fluid) transfusion apparatus is formed by combining a PVC conduit and other auxiliary parts. In the process, due to the characteristic of easy degradation of polyvinyl chloride, once the polyvinyl chloride is degraded, the polyvinyl chloride cannot pass the strict standard of the national standard GB15593 for medical blood (fluid) transfusion instruments. Such stabilizers must therefore possess efficient thermal stability properties.
Good transparency is required because transfusion (fluid) instruments require special care when used. In addition, according to the national standards of the people's republic of China, medical instruments for blood (liquid) transfusion need to be sterilized by high-temperature and high-pressure steam at 121 ℃. Ordinary PVC material can take place water smoke after this process and analyse white and bag body adhesion scheduling problem, water smoke is analyzed out and is whited if not solve then probably cause the problem of can't see the interior state of container clearly, bag body adhesion then can lead to can't leading to in the use filling with when serious probably causing the bag body damage seriously then. In general, manufacturers add methyl silicone oil or benzyl silicone oil to PVC to prevent high-temperature adhesion, and add surfactants such as span-80 to solve the problem of water vapor whitening.
However, the commonly used surfactant additives have high hydrophilicity and low molecular weight, and the results of ultraviolet absorption tests on the transfusion (fluid) instrument leaching liquor according to national standards are high, which affects the product quality; and the refractive index of the silicone oil substances is greatly different from that of PVC, and the opacity of the product can be seriously influenced after the silicone oil substances are added.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects in the prior art and provide an improved calcium-magnesium-zinc liquid stabilizer which is added into soft PVC, so that the soft PVC has excellent transparency, high-temperature adhesion resistance and water-fog whitening resistance.
Therefore, the invention adopts the following technical scheme: a calcium magnesium zinc liquid stabilizer comprises zinc salt of organic acid, calcium oleate, magnesium salt of organic acid, segmented polyethylene oxide-polypropylene oxide ricinoleate with molecular weight of 2400-2600 and solvent;
the block polyethylene oxide-polypropylene oxide ricinoleate has the molar ratio of EO to PO of 1: 3-4.
Ricinoleic acid is a vegetable oil product, and derivatives of ricinoleic acid can be used as substitutes of petroleum products, and can provide good processing performance and thermal stability for PVC in a thermal stabilizer. In the existing data, ricinoleic acid derivatives with small molecular weight are generally used, are easy to be used up in the degradation process of PVC, and have no long-lasting excellent lubricating property and stripping property on PVC.
Castor oil polyoxyethylene ether (EL-80) is a common nonionic surfactant, has good acid and alkali resistance, good compatibilization performance, extremely strong emulsifying property and good hydrophilicity, but has poor compatibility with PVC materials, and has no reliable application in PVC.
The segmented polyethylene oxide-polypropylene oxide ricinoleate with the molecular weight of about 2500 has good heat resistance and chemical stability, is suitable for long-time processing, can obtain lipophilic or hydrophilic trend according to the change of the proportion of EO and PO in a segmented structure, is similar to long-chain structures such as PVC and a plasticizer thereof in soft PVC, has good compatibility with PVC, is not easy to precipitate, and has a certain solubilizing effect.
The calcium-magnesium-zinc liquid stabilizer provided by the invention is added into PVC, and provides good and durable processing performance and stripping performance of PVC.
The block polyethylene oxide-polypropylene oxide ricinoleate used in the invention has a limited molecular weight of about 2500. According to the experiment, if the molecular weight is more than 4000, the high-temperature blocking resistance and the water fog whitening resistance can be provided, but the transparency of the product is affected, and the high-temperature blocking resistance and water fog whitening resistance can be used in non-high-transparency products.
Preferably, the calcium, magnesium and zinc liquid stabilizer comprises the following components in parts by weight:
most preferably, the calcium, magnesium and zinc liquid stabilizer comprises the following components in parts by weight:
further, the zinc salt of the organic acid is one or a mixture of two of zinc isooctanoate, zinc oleate and zinc 4-tert-butyl benzoate. Compared with calcium salt, the organic acid magnesium salt is alkaline earth metal salt with better transparency, and can provide good transparency when being compounded with liquid calcium salt.
Further, the liquid calcium oleate contains a solvent, preferably, the liquid calcium oleate contains 40-60% of the solvent by mass percent, which is favorable for uniform dispersion.
Further, the organic acid magnesium salt is one of magnesium stearate and magnesium laurate.
Further, the preparation method of the block polyethylene oxide-polypropylene oxide ricinoleate comprises the following steps:
placing 1mol equivalent of analytically pure ricinoleic acid into a clean, dry and sealed reactor, adding 0.05mol of powdery potassium hydroxide, stirring, heating a spacer bush of the reactor to 150 +/-5 ℃ under normal pressure, keeping the temperature, introducing pure nitrogen to replace air in the reactor and a pipeline, slowly adding 40mol equivalents of a mixture of EO and PO, wherein the molar ratio of EO to PO is 1: and 3-4, keeping the pressure at 0.2 +/-0.05 MPa, continuously reducing the pressure after the gas is introduced, continuously stirring until the pressure is constant, keeping the constant temperature and the constant pressure for 1.5-2.5 hours, cooling, releasing the pressure in the reactor, and purifying to obtain the segmented polyethylene oxide-polypropylene oxide ricinoleate with the molecular weight of 2400 minus or plus 2600.
Further, the solvent is one or a mixed solvent of more than two of kerosene, liquid paraffin, diethylene glycol monobutyl ether, epoxidized soybean oil, dioctyl terephthalate and trioctyl citrate. If the stabilizer is used alone, the problems of uneven dispersion or sedimentation of the stabilizer are often caused, and in order to increase the dissolution and dispersion performance among the main stabilizers and the good liquid fluidity and processing performance of the stabilizer during use, a plurality of solvents are preferably mixed to improve the flow performance of the liquid stabilizer.
The invention also provides an application of the calcium-magnesium-zinc liquid stabilizer, which is to add the calcium-magnesium-zinc liquid stabilizer into soft PVC to prepare a medical blood transfusion or infusion container film.
The calcium-magnesium-zinc liquid stabilizer has the advantages of good synergistic performance of all components, good compatibility with polyvinyl chloride resin, no toxicity and environmental protection. The calcium-magnesium-zinc liquid stabilizer provided by the invention is added into soft PVC, has excellent transparency, high-temperature adhesion resistance and water-fog-whitening resistance for the soft PVC, and has an outstanding solving effect on the problems of the existing blood transfusion (liquid) instruments in practical application.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
350g of zinc isooctanoate, 250g of zinc 4-tert-butylbenzoate, 300g of liquid calcium oleate, 300g of magnesium laurate, 100g of diethylene glycol monobutyl ether, 400g of kerosene and 300g of block polyethylene oxide-polypropylene oxide ricinoleate.
The above formula is mixed into a uniform stabilizer and then is kept stand for later use.
The PVC resin comprises the following components in percentage by weight: 100kg of PVC (SG-1000), 35kg of dioctyl terephthalate, 10kg of epoxidized soybean oil (B-22), 0.5kg of antifogging agent AF and 3kg of stabilizing agent. The formula is put into a high-speed mixer for high-speed hot mixing, and the final temperature of the hot mixing is 125 ℃. And (5) entering cold mixing for later use.
And (3) performing single-screw granulation on the cooled powder, wherein the temperature of a granulation die head is 168 ℃, and the detection value during melting compaction is not more than 12.5 pa. And (5) after granulation, screening by a vibrating screen and collecting.
The collected granules are put into a single-screw open mill, and the maximum smelting temperature is 178 ℃. And (4) after smelting, feeding the molten steel into a five-roller calender while the molten steel is hot, calendering to form a film, and quenching by a cooling roller. The example film 1 was obtained with a thickness of 0.25 mm.
In the following examples and comparative examples, except for the compounding ratio of the stabilizer, the same compounding ratio and process parameters as those in example 1 were used to obtain a PVC resin composition, pellets and a film.
Comparative example 1
35g of zinc isooctanoate, 25g of zinc 4-tert-butylbenzoate, 30g of liquid calcium oleate, 30g of magnesium laurate, 10g of diethylene glycol monobutyl ether, 40g of kerosene and 30g of phenylmethylsiloxane.
Because the specific raw materials in the examples are lacked in the comparative examples, the problem of stabilizer sedimentation can occur due to insufficient solubility, and the stabilizer can be heated and mixed uniformly before feeding.
Example 2
The raw material ratio of the stabilizer is as follows: 60g of 4-tert-butyl zinc benzoate, 30g of liquid calcium oleate, 30g of magnesium stearate, 30g of block polyethylene oxide-polypropylene oxide ricinoleate, 20g of dioctyl terephthalate, 5g of diethylene glycol monobutyl ether and 25g of liquid paraffin.
Comparative example 2
The raw material ratio of the stabilizer is as follows: 60g of zinc 4-tert-butylbenzoate, 30g of liquid calcium oleate, 30g of magnesium stearate, 30g of phenylmethylsiloxane, 20g of dioctyl terephthalate, 5g of diethylene glycol monobutyl ether and 25g of liquid paraffin.
Example 3
The raw material ratio of the stabilizer is as follows: 35g of zinc oleate, 25g of zinc 4-tert-butylbenzoate, 30g of liquid calcium oleate, 30g of magnesium stearate, 30g of segmented polyethylene oxide-polypropylene oxide ricinoleate, 20g of dioctyl terephthalate, 5g of diethylene glycol monobutyl ether and 25g of liquid paraffin.
Example 4
The raw material ratio of the stabilizer is as follows: 60g of zinc iso-octoate, 30g of liquid calcium oleate, 30g of magnesium laurate, 30g of block polyethylene oxide-polypropylene oxide ricinoleate, 30g of dioctyl terephthalate, 15g of trioctyl citrate and 5g of liquid paraffin.
And placing the obtained film on a glass sheet, placing the glass sheet into a constant-temperature oven at 180 ℃, and recording the color change state and the static thermal stability time. The test results are shown in Table 1.
TABLE 1 static thermal stability time
| Film numbering | Initial whiteness (%) | Yellowing time (min) | Static thermal stability time (min) |
| Example 1 | 93 | 35 | 47 |
| Comparative example 1 | 90 | 29 | 42 |
| Example 2 | 93 | 35 | 46 |
| Comparative example 2 | 90 | 33 | 41 |
| Example 3 | 90 | 35 | 43 |
| Example 4 | 95 | 33 | 46 |
The resulting films were aligned in pairs and placed in a high frequency sealer at 220V for 5 seconds to form 15cm by 25cm square bags of liquid, fitted with catheter connectors. Stacking 10 bags in order, putting the bags in a constant-temperature steam sterilizing pot, setting the temperature at 121 ℃, and sterilizing for 30 minutes. And (3) taking out the bag bodies after the disinfection is finished, cooling, taking out the upper 5 bag bodies, placing the bag bodies in an environment with normal temperature and normal pressure and humidity of 50%, and detecting and recording average haze values of the bag bodies after 2 hours, 12 hours and 24 hours. The test results are shown in Table 2.
Take out 5 bag bodies down in addition, connect the internal diameter 2.5mm pipe, the vertical bag body, from the water potential of 5cm height, rely on gravity to flow into the bag body with deionized water nature, note the time that the bag body was filled to deionized water. The test results are shown in Table 3.
TABLE 2 haze values after different periods (%)
TABLE 3 deionized water filling time (seconds)
From the above table, it can be concluded that the calcium-magnesium-zinc liquid stabilizer provided by the invention has good heat resistance, and meanwhile, the PVC film product prepared by the stabilizer has good water mist resistance and bag body adhesion resistance after high-pressure steam sterilization.
Example 5
The raw material ratio of the stabilizer is as follows: 30g of zinc 4-tert-butylbenzoate, 10g of zinc oleate, 35g of liquid calcium oleate, 25g of magnesium laurate, 50g of block polyethylene oxide-polypropylene oxide ricinoleate, 30g of dioctyl terephthalate, 15g of trioctyl citrate and 5g of liquid paraffin.
Comparative example 5
The raw material ratio of the stabilizer is as follows: 30g of zinc 4-tert-butylbenzoate, 10g of zinc oleate, 35g of liquid calcium oleate, 25g of magnesium laurate, 50g of castor oil polyoxyethylene ether (molecular weight is about 1500), 30g of dioctyl terephthalate, 15g of trioctyl citrate and 5g of liquid paraffin.
The films obtained by rolling in example 5 and comparative example 5 were immersed in 20g/L calcium chloride solution, sealed and left standing in a room at normal temperature and pressure for about one week, and the surface condition was observed.
It is observed that the aqueous solution in example 5 is clear and transparent, but the solution in comparative example 5 has a small amount of turbid substances on the surface of the PVC film, and analysis shows that PVC precipitates are flocculated with calcium chloride, so that the conclusion is drawn that the block polyethylene oxide-polypropylene oxide ricinoleate has good compatibility in PVC materials and is not easy to precipitate compared with castor oil polyoxyethylene ether.
Example 6
The raw material ratio of the stabilizer is as follows: 35g of zinc isooctanoate, 25g of zinc 4-tert-butylbenzoate, 30g of liquid calcium oleate, 30g of magnesium laurate, 20g of block polyethylene oxide-polypropylene oxide ricinoleate, 10g of diethylene glycol monobutyl ether and 50g of kerosene.
Example 7
The raw material ratio of the stabilizer is as follows: 35g of zinc isooctanoate, 25g of zinc 4-tert-butylbenzoate, 30g of liquid calcium oleate, 30g of magnesium laurate, 50g of block polyethylene oxide-polypropylene oxide ricinoleate, 10g of diethylene glycol monobutyl ether and 20g of kerosene.
Example 8
The raw material ratio of the stabilizer is as follows: 60g of 4-tert-butyl zinc benzoate, 30g of liquid calcium oleate, 30g of magnesium laurate, 20g of block polyethylene oxide-polypropylene oxide ricinoleate, 30g of dioctyl terephthalate, 15g of trioctyl citrate and 15g of liquid paraffin.
Example 9
The raw material ratio of the stabilizer is as follows: 60g of 4-tert-butyl zinc benzoate, 30g of liquid calcium oleate, 30g of magnesium laurate, 50g of block polyethylene oxide-polypropylene oxide ricinoleate, 20g of dioctyl terephthalate and 10g of trioctyl citrate.
The PVC resin comprises the following components in percentage by weight: 100kg of PVC (SG-1000), 32kg of dioctyl terephthalate, 5kg of epoxidized soybean oil (B-22) and 3kg of stabilizing agent. Examples 6, 7, 8 and 9 were compounded according to the above formulation and compression molded at 155 ℃ for 5 minutes to form tablets. The number of false fish eyes per square centimeter was recorded. The results are summarized in Table 4.
TABLE 4 fish eyes per square centimeter (pieces/centimeter)2)
It can be concluded from table 4 that the block polyethylene oxide-polypropylene oxide ricinoleate has a certain plasticizing promoting effect on PVC, and a small amount of block polyethylene oxide-polypropylene oxide ricinoleate can reduce the number of fish eyes or crystal grains in PVC products, thereby improving the product quality.
It should be understood that although the present invention has been clearly illustrated by the foregoing embodiments, various changes and modifications may be made therein by those skilled in the art without departing from the spirit and scope of the invention, and it is intended to cover all such changes and modifications as fall within the scope of the appended claims.
Claims (9)
1. A calcium magnesium zinc liquid stabilizer is characterized by comprising zinc salt of organic acid, calcium oleate, magnesium salt of organic acid, segmented polyethylene oxide-polypropylene oxide ricinoleate with molecular weight of 2400-2600 and solvent;
the block polyethylene oxide-polypropylene oxide ricinoleate has the molar ratio of EO to PO of 1: 3-4;
the calcium, magnesium and zinc liquid stabilizer comprises the following components in parts by weight:
20-60 parts of organic acid zinc salt;
15-25 parts of liquid calcium oleate;
10-20 parts of organic acid magnesium salt;
10-20 parts of segmented polyethylene oxide-polypropylene oxide ricinoleate with the molecular weight of 2400-2600;
5-45 parts of a solvent.
2. The calcium magnesium zinc liquid stabilizer according to claim 1, characterized by comprising, in parts by weight:
30-50 parts of organic acid zinc salt;
20 parts of liquid calcium oleate;
10-15 parts of organic acid magnesium salt;
15 parts of segmented polyethylene oxide-polypropylene oxide ricinoleate with the molecular weight of 2400-2600;
5-25 parts of a solvent.
3. The Ca-Mg-Zn liquid stabilizer according to any one of claims 1 to 2, wherein the zinc salt of organic acid is one or a mixture of two of zinc isooctanoate, zinc oleate and zinc 4-tert-butylbenzoate.
4. The calcium magnesium zinc liquid stabilizer according to any one of claims 1 to 2, characterized in that the liquid calcium oleate contains a solvent.
5. The calcium magnesium zinc liquid stabilizer according to claim 4, wherein the liquid calcium oleate contains 40 to 60 mass% of solvent.
6. The calcium-magnesium-zinc liquid stabilizer according to any one of claims 1 to 2, wherein the magnesium salt of an organic acid is one of magnesium stearate and magnesium laurate.
7. The calcium magnesium zinc liquid stabilizer according to any one of claims 1 to 2, characterized in that the block polyethylene oxide-polypropylene oxide ricinoleate is prepared by the following method:
placing 1mol equivalent of analytically pure ricinoleic acid into a clean, dry and sealed reactor, adding 0.05mol of powdery potassium hydroxide, stirring, heating a spacer bush of the reactor to 150 +/-5 ℃ under normal pressure, keeping the temperature, introducing pure nitrogen to replace air in the reactor and a pipeline, slowly adding 40mol equivalents of a mixture of EO and PO, wherein the molar ratio of EO to PO is 1: and 3-4, keeping the pressure at 0.2 +/-0.05 MPa, continuously reducing the pressure after the gas is introduced, continuously stirring until the pressure is constant, keeping the constant temperature and the constant pressure for 1.5-2.5 hours, cooling, releasing the pressure in the reactor, and purifying to obtain the segmented polyethylene oxide-polypropylene oxide ricinoleate with the molecular weight of 2400 minus or plus 2600.
8. The calcium-magnesium-zinc liquid stabilizer according to any one of claims 1 to 2, wherein the solvent is one or a mixed solvent of more than two of kerosene, liquid paraffin, diethylene glycol monobutyl ether, epoxidized soybean oil, dioctyl terephthalate and trioctyl citrate.
9. Use of a liquid stabilizer of calcium, magnesium and zinc according to any one of claims 1 to 8, characterized in that the liquid stabilizer of calcium, magnesium and zinc is added to flexible PVC to form a film for medical blood transfusion or infusion containers.
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| CN102977503A (en) * | 2012-12-07 | 2013-03-20 | 青岛鑫万通塑业发展有限公司 | PVC (polyvinyl chloride) soap composite heat stabilizer |
| CN104387695A (en) * | 2014-11-06 | 2015-03-04 | 安徽省三乐门窗幕墙工程有限公司 | High-strength PVC (polyvinyl chloride) wood-plastic composite material and preparation method thereof |
| CN104292710A (en) * | 2014-11-06 | 2015-01-21 | 安徽省三乐门窗幕墙工程有限公司 | Waterproof PVC (polyvinyl chloride) wood-plastic composite material and preparation method thereof |
| JP6179740B1 (en) * | 2016-03-22 | 2017-08-16 | 堺化学工業株式会社 | Liquid stabilizer for soft vinyl chloride resin, soft vinyl chloride resin composition using the stabilizer, and molded article formed from the composition |
| CN106398038B (en) * | 2016-08-31 | 2018-08-28 | 湖北犇星化工有限责任公司 | A kind of organotin compound stabilizer and preparation method thereof being used to prepare PVC |
| CN106566128A (en) * | 2016-10-28 | 2017-04-19 | 祖兴保 | Triethyl phosphate composite environment-friendly stabilizer for PVC and preparation method thereof |
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2018
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