CN115926339A - Organic zincate modified high-transparency PVC (polyvinyl chloride) film and preparation method thereof - Google Patents

Organic zincate modified high-transparency PVC (polyvinyl chloride) film and preparation method thereof Download PDF

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CN115926339A
CN115926339A CN202211534452.9A CN202211534452A CN115926339A CN 115926339 A CN115926339 A CN 115926339A CN 202211534452 A CN202211534452 A CN 202211534452A CN 115926339 A CN115926339 A CN 115926339A
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CN115926339B (en
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林东坡
陈金河
孙海青
熊本进
蔡建文
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Baierluohe New Material Technology Co ltd
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Abstract

The invention discloses an organic zincate modified high-transparency PVC film and a preparation method thereof, wherein the organic zincate modified high-transparency PVC film comprises the following components: 0.1-0.5 part of organic zinc compound, 100 parts of PVC resin, 1-2 parts of calcium-zinc stabilizer and 15-50 parts of plasticizer, wherein the organic zinc compound is prepared by the reaction of polyvinyl alcohol and zinc stearate. According to the organic zinc compound modified high-transparency PVC film, the organic zinc compound with proper dosage is added in the formula, so that the compatibility among all components is improved, and the modified organic zinc compound has small molecular linear length and refractive index close to that of a PVC resin matrix, so that the transparency of the PVC film is obviously improved, and the PVC film has a lower haze value in a test result; the preparation method of the organic zincate modified high-transparency PVC film has the advantages of simple operation steps, high implementation feasibility, cheap and easily-obtained raw materials and good economic practicality.

Description

Organic zincate modified high-transparency PVC (polyvinyl chloride) film and preparation method thereof
Technical Field
The invention belongs to the technical field of high polymer packaging materials, and particularly relates to an organic zincate modified high-transparency PVC film and a preparation method thereof.
Background
The PVC (polyvinyl chloride) product is a universal packaging material with the highest domestic productivity, and has wide application range and market prospect. The transparent PVC product has the advantages of high transparency, less crystal point impurities, low cost and the like, and is widely applied to various high-grade packaging material industries, such as food and medicine packaging boxes, high-grade daily necessity packaging, artware packaging materials and the like.
In recent years, under the influence of price fluctuation of petroleum and price fluctuation of a large amount of chemical raw materials, in order to optimize product cost and further improve the competitiveness of transparent PVC products compared with products such as transparent PET, transparent PP and the like, an additive capable of further improving product transparency without increasing product cost is urgently needed by vast transparent PVC product production enterprises.
The selection of the raw material type of the transparent PVC film product requires that the raw material has certain PVC compatibility and similar refractive index, and also requires certain stability and lubricity. The zinc stearate has good lubricity and stability and can be used as an excellent processing aid for transparent PVC film products, but the zinc stearate lacking modification has a too prominent lubricating effect, so that the problems of poor compatibility with other raw material components of PVC products, difficulty in processing, low stability and the like are easily caused, and therefore the zinc stearate cannot be widely applied to PVC transparent products.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide an organic zinc compound modified high-transparency PVC film and a preparation method thereof, wherein the compatibility among all components is improved by adding an appropriate amount of organic zinc compound into a formula, and the modified organic zinc compound has small molecular linear length and refractive index close to that of a PVC resin matrix, so that the transparency of the PVC film is obviously improved, and the modified organic zinc compound has a lower haze value in a test result; the preparation method of the organic zincate modified high-transparency PVC film has the advantages of simple operation steps, high implementation feasibility, cheap and easily-obtained raw materials and good economic practicality.
One of the purposes of the invention is to design an organic zincate modified high-transparency PVC film, which comprises the following components: 0.1-0.5 part of organic zinc compound, 100 parts of PVC resin, 1-2 parts of calcium zinc stabilizer and 15-50 parts of plasticizer, wherein the organic zinc compound is prepared by the reaction of polyvinyl alcohol and zinc stearate.
The preferable technical scheme is that the polymerization degree of the PVC resin is 1000-1300.
The preferable technical proposal is that the plasticizer is one or more of dioctyl terephthalate, epoxidized soybean oil and liquid phosphite ester.
The second purpose of the invention is to design a preparation method of the organic zincate modified high-transparency PVC film, which is used for preparing the organic zincate modified high-transparency PVC film and comprises the following steps:
s1: preparing polyvinyl alcohol and water into a polyvinyl alcohol aqueous solution according to a certain mass feed ratio, and preparing zinc stearate and a solvent into a zinc stearate solution according to a certain mass feed ratio;
s2: slowly dripping zinc stearate solution into polyvinyl alcohol aqueous solution, stirring and reacting for 2-4 h at the temperature of 60-70 ℃, filtering, washing filter cakes and drying the reaction mixture in sequence to obtain an organic zincate;
s3: adding 0.1-0.5 part of organic zinc compound, 100 parts of PVC resin, 1-2 parts of calcium-zinc stabilizer and 15-50 parts of plasticizer into a high-speed stirrer, and uniformly mixing to obtain a raw material mixture;
s4: and (4) preparing the raw material mixture prepared in the step (S3) into the organic zinc compound modified high-transparency PVC film in an open mill.
Preferably, the step S1 specifically comprises the following operations: stirring polyvinyl alcohol and water according to a mass ratio of 1; stirring zinc stearate and a solvent for 4-6 h at the temperature of 50-70 ℃ according to the mass ratio of 1.
In the preferable technical scheme, in the step S3, the mixing temperature is 60-100 ℃, and the stirring time is 5-15 min.
In the preferable technical scheme, in the step S4, the working condition of the open mill is 175-185 ℃, and the processing time is 2-5 min.
The invention has the advantages and beneficial effects that:
1. according to the organic zinc compound modified high-transparency PVC film, the organic zinc compound with proper dosage is added in the formula, so that the compatibility among all components is improved, and the modified organic zinc compound has small molecular linear length and refractive index close to that of a PVC resin matrix, so that the transparency of the PVC film is obviously improved, and the PVC film has a lower haze value in a test result.
2. The preparation method of the organic zincate modified high-transparency PVC film has the advantages of simple operation steps, high implementation feasibility, cheap and easily-obtained raw materials and good economic practicality.
Detailed Description
The following further describes embodiments of the present invention with reference to examples. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Example 1
An organic zincate modified high-transparency PVC film comprises the following components: 0.1 part of organic zinc compound, 100 parts of PVC resin, 1-2 parts of calcium-zinc stabilizer (CT 362P/2 brand, produced by Bailroch New Material science and technology Co., ltd.), and 15 parts of plasticizer (dioctyl terephthalate, DOTP).
The preparation method of the organic zincate modified high-transparency PVC film in the embodiment comprises the following steps:
(1) Heating and stirring polyvinyl alcohol (PVA) and water at the mass ratio of 1;
(2) Heating and stirring zinc stearate particles and a xylene solution for 4 hours at the temperature of 70 ℃ according to the mass ratio of 1;
(3) Slowly dropwise adding a zinc stearate solution into a PVA (polyvinyl alcohol) aqueous solution, heating and stirring at the temperature of 70 ℃ for reaction for 2 hours to separate out white particles, and sequentially filtering, washing and drying a filter cake to obtain organic zincate powder;
(4) Adding 0.1 part of the organic zincate powder prepared in the step (3), 100 parts of PVC resin, 1-2 parts of CT 362P/2 of calcium-zinc stabilizer and 15 parts of DOTP plasticizer into a high-speed stirrer, and uniformly mixing to obtain a raw material mixture, wherein the mixing temperature is 60 ℃, and the stirring time is 15min;
(5) And (3) putting the raw material mixture prepared in the step (4) into a two-roll open mill, and preparing the PVC film with the length/width/thickness of 10cm, 10cm and 1mm at the temperature of 175 ℃ and the processing time of 5min.
Example 2
An organic zincate modified high-transparency PVC film comprises the following components: 0.3 part of organic zinc compound, 100 parts of PVC resin, 1.5 parts of calcium-zinc stabilizer (CT 362P/2 brand, produced by Bailroch New Material science and technology Co., ltd.), and 30 parts of plasticizer (dioctyl terephthalate, DOTP).
The preparation method of the organic zincate modified high-transparency PVC film in the embodiment comprises the following steps:
(1) Heating and stirring polyvinyl alcohol (PVA) and water according to a mass ratio of 1;
(2) Heating and stirring zinc stearate particles and a xylene solution for 5 hours at the temperature of 65 ℃ according to the mass ratio of 1;
(3) Slowly dropwise adding a zinc stearate solution into a PVA (polyvinyl alcohol) aqueous solution, heating and stirring at 65 ℃ for reaction for 3 hours to separate out white particles, and sequentially filtering, washing a filter cake and drying the reaction mixture to obtain organic zincate powder;
(4) Adding 0.3 part of the organic zincate powder prepared in the step (3), 100 parts of PVC resin, 1.5 parts of CT 362P/2.5 parts of calcium-zinc stabilizer and 30 parts of DOTP plasticizer into a high-speed stirrer, and uniformly mixing to obtain a raw material mixture, wherein the mixing temperature is 80 ℃, and the stirring time is 10min;
(5) Preparing a PVC film with the length/width/thickness of 10cm/10 cm/1mm in a two-roll open mill at the temperature of 180 ℃ and the processing time of 5min from the raw material mixture prepared in the step (4).
Example 3
An organic zincate modified high-transparency PVC film comprises the following components: 0.5 part of organic zinc compound, 100 parts of PVC resin, 2 parts of calcium zinc stabilizer (CT 362P/2, product name of Baileroch New Material science and technology Co., ltd.) and 50 parts of plasticizer (dioctyl terephthalate, DOTP).
The preparation method of the organic zincate modified high-transparency PVC film in the embodiment comprises the following steps:
(1) Heating and stirring polyvinyl alcohol (PVA) and water according to a mass ratio of 1;
(2) Heating and stirring zinc stearate particles and a xylene solution for 6 hours at the temperature of 60 ℃ according to the mass ratio of 1;
(3) Slowly dropwise adding a zinc stearate solution into a PVA (polyvinyl alcohol) aqueous solution, heating and stirring at the temperature of 60 ℃ for reaction for 4 hours to separate out white particles, and sequentially filtering, washing and drying a filter cake to obtain organic zincate powder;
(4) Adding 0.5 part of the organic zincate powder prepared in the step (3), 100 parts of PVC resin, 362P/2 parts of calcium zinc stabilizer CT/2 and 50 parts of plasticizer DOTP into a high-speed stirrer, and uniformly mixing to obtain a raw material mixture, wherein the mixing temperature is 80 ℃, and the stirring time is 10min;
(5) The raw material mixture prepared in step (4) was placed in a two-roll mill and processed at 185 ℃ for 2min to prepare a PVC film having a length/width/thickness of 1 cm by 10cm by 1 mm.
In order to more clearly illustrate the advantageous effects of the present invention, the present invention also provides PVC films to which no organozincate is added and PVC films to which only zinc stearate is added as comparative examples, and the PVC films in comparative examples 1 to 6 and the organozincate-modified high transparency PVC films in examples 1 to 3 have the composition shown in table 1:
TABLE 1 ingredient List of organozincate-modified high-clarity PVC films of examples 1-3 and PVC films of comparative examples 1-6
Figure BDA0003977030110000051
The method for preparing the thin film of comparative example 1, comprising the steps of:
(1) 100 parts of PVC resin, 1-2 parts of CT 362P/2 parts of calcium-zinc stabilizer and 15 parts of DOTP plasticizer are added into a high-speed stirrer to be uniformly mixed to obtain a raw material mixture, the mixing temperature is 60 ℃, and the stirring time is 15min;
(2) Preparing a PVC film with the length/width/thickness of 10cm × 1mm in a two-roll open mill by using the raw material mixture prepared in the step (1) at the temperature of 175 ℃ and the processing time of 5min.
The films of comparative examples 2 to 6 were prepared in the same manner as in comparative example 1.
The organic zincate-modified high-transparency PVC films prepared in examples 1 to 3 and the PVC films prepared in comparative examples 1 to 3 are respectively kept stand for 24 hours at room temperature for state adjustment, then the corresponding PVC films are subjected to haze test according to GB/T2410-2008 'determination of transparent plastic transmittance and haze', the lower the haze value is, the higher the transparency of the PVC film sample is reflected, and the test results are shown in Table 2:
TABLE 2 results of surface haze test of the organozincate-modified high-transparency PVC films of examples 1 to 3 and the PVC films of comparative examples 1 to 6
Figure BDA0003977030110000061
As can be seen from the haze test results in table 2: the PVC films to which the organic zincate was added in examples 1 to 3 had lower haze values, the PVC films to which the organic zincate was not added in comparative examples 1 to 3 had higher haze values than the PVC films to which the organic zincate was added in examples 1 to 3, and the PVC films to which only zinc stearate was added in comparative examples 4 to 6 had higher haze values than the PVC films in examples 1 to 3, and thus, it was found from the test results that the PVC film samples had higher transparency due to the addition of the organic zincate, achieving the object of the invention.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, it is possible to make various improvements and modifications without departing from the technical principle of the present invention, and these improvements and modifications should also be considered as the protection scope of the present invention.

Claims (7)

1. An organic zincate modified high-transparency PVC film is characterized by comprising the following components in percentage by weight: 0.1-0.5 part of organic zinc compound, 100 parts of PVC resin, 1-2 parts of calcium zinc stabilizer and 15-50 parts of plasticizer, wherein the organic zinc compound is prepared by the reaction of polyvinyl alcohol and zinc stearate.
2. The organozincate-modified high-transparency PVC film according to claim 1, wherein the degree of polymerization of the PVC resin is 1000 to 1300.
3. The organozincate-modified high transparency PVC film according to claim 1 wherein the plasticizer is one or more of dioctyl terephthalate, epoxidized soybean oil, liquid phosphite.
4. A method for preparing an organozincate-modified high-transparency PVC film, which is used for preparing the organozincate-modified high-transparency PVC film according to any one of claims 1 to 3, comprising the steps of:
s1: preparing polyvinyl alcohol and water into a polyvinyl alcohol aqueous solution according to a certain mass feed ratio, and preparing zinc stearate and a solvent into a zinc stearate solution according to a certain mass feed ratio;
s2: slowly dripping zinc stearate solution into polyvinyl alcohol aqueous solution, stirring and reacting for 2-4 h at the temperature of 60-70 ℃, filtering, washing filter cakes and drying the reaction mixture in sequence to obtain an organic zincate;
s3: adding 0.1-0.5 part of organic zinc compound, 100 parts of PVC resin, 1-2 parts of calcium-zinc stabilizer and 15-50 parts of plasticizer into a high-speed stirrer, and uniformly mixing to obtain a raw material mixture;
s4: and (4) preparing the raw material mixture prepared in the step (S3) into the organic zinc compound modified high-transparency PVC film in an open mill.
5. The method for preparing the organozincate-modified high-transparency PVC film according to claim 4, wherein the step S1 is specifically performed by: stirring polyvinyl alcohol and water according to a mass ratio of 1; stirring zinc stearate and a solvent for 4-6 h at the temperature of 50-70 ℃ according to the mass ratio of 1.
6. The method for preparing an organozincate-modified high-transparency PVC film according to claim 4, wherein the mixing temperature is 60 to 100 ℃ and the stirring time is 5 to 15min in the step S3.
7. The method for preparing organozincate-modified high-transparency PVC film according to claim 4, wherein the open mill is operated at 175 to 185 ℃ for 2 to 5min in the step S4.
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