WO2017182003A1

WO2017182003A1 - Polyvinyl chloride low-temperature toughening modifier and polyvinyl chloride composition containing low-temperature toughening modifier

Info

Publication number: WO2017182003A1
Application number: PCT/CN2017/081687
Authority: WO
Inventors: 赵东日; 路恩斌; 徐峰; 边增和
Original assignee: 山东日科化学股份有限公司
Priority date: 2016-04-23
Filing date: 2017-04-24
Publication date: 2017-10-26
Also published as: CN105693891A

Abstract

Disclosed in the present invention are a polyvinyl chloride low-temperature toughening modifier and a polyvinyl chloride composition containing the low-temperature toughening modifier. The low-temperature toughening modifier is rubber powder of which the elongation at break is 1000% to 1600%, the Shore hardness is greater than 53.0 HA and the tensile strength is greater than 9.0 MPa. The polyvinyl chloride composition comprises the following raw material components in parts by weight: (a) 100 parts of polyvinyl chloride resin; (b) 1 to 30 parts of low-temperature toughening modifier; (c) 0.5 to 5 parts of stabilizer; (d) 0 to 50 parts of filler; (e) 0 to 50 parts of wood flour; (f) 0 to 10 parts of acrylate polymer; (g) 0 to 20 parts of anti-impact modifier; (h) 0 to 5 parts of lubricant; and (i) 0 to 10 parts of pigment. By modifying PVC by using the low-temperature toughening modifier, the elongation at break of a PVC hard product can be greatly improved without affecting the hardness and the tensile strength of the PVC.

Description

Polyvinyl chloride low temperature toughening modifier and polyvinyl chloride composition containing the low temperature toughening modifier

Technical field

The invention relates to the technical field of polyvinyl chloride modifiers, in particular to a low temperature toughening modifier for polyvinyl chloride.

Background technique

Generally speaking, polyvinyl chloride (PVC) resin has the following disadvantages: 1. poor processability; 2. poor low temperature impact strength; 3. poor thermal stability; 4. poor low temperature toughness. Various methods have been invented to improve the shortcomings of PVC, such as: people invented processing aids to improve the processing properties of PVC; invented impact modifiers to improve the low temperature impact properties of PVC; invented heat stabilizers to improve PVC The thermal stability energy, invented a low elongation toughness modifier of high elongation at break to improve the low temperature toughness of PVC (for example, Patent Document: Application No. 201210129071.2; Application No. 201310169266.4; Application No. 201310169434.X), but the inventor further It has been found that although the high elongation toughness low elongation toughness modifier can solve the problem of poor toughness of PVC, it can greatly improve the elongation at break of PVC, but the low elongation toughness due to high elongation at break The tensile strength of the agent is low and the hardness is low. The elongation at break of the PVC product modified with the low elongation toughness modifier with high elongation at break is greatly improved, but the hardness and tensile strength are also obvious. The decline has been made.

For a long time, there is a big misunderstanding in the field of PVC modification. It is wrong to think that the notched impact strength and toughness of PVC are the same concept, so people invented the terpolymer of styrene-methyl methacrylate-butadiene. (MBS) and acrylate type of acrylic impact modifier (AIM) to improve the notched impact strength and elongation at break of PVC. However, later practice found that the two types of core-shell graft copolymers (MBS, AIM) can significantly improve the notched impact strength of PVC, but the elongation at break of PVC is not obvious. That is, the toughness of PVC has not been significantly improved. The inventors have found through a large number of experiments that although there is a certain relationship between the notched impact strength of PVC and the toughness, that is, the elongation at break, there are still differences between the two. To improve the notched impact strength of PVC, MBS and AIM with core-shell structure can be used, but due to the elongation of AIM and MBS The long rate is very low (usually less than 250%), and it is difficult to greatly increase the elongation at break of PVC by using MBS and AIM.

The inventors have found that the impact strength is closely related to the phase structure of the material, and the toughness is closely related to the elongation at break of the material. Therefore, in order to improve the toughness of the polymer material, it is necessary to increase the elongation at break of the material, and the inventors have found In order to increase the elongation at break of the polymer material, it is necessary to increase the elongation at break of the low temperature toughening modifier. However, while the elongation at break of the low temperature toughening modifier increases, the hardness decreases. The decrease in the hardness of the low temperature toughening modifier causes polymer materials such as PVC to be modified with low temperature toughening modifiers, although the toughness is improved, but the hardness and tensile strength are reduced. This is any one. Materials engineers are reluctant to see the results. For material engineers, the ideal low temperature toughening modifier should greatly improve the toughness, ie, elongation at break, of PVC while maintaining the hardness and tensile strength of PVC. Meanwhile, if the elongation at break of a low temperature toughening modifier is high, if the hardness and tensile strength of the low temperature toughening modifier decrease, it will cause agglomeration of the low temperature toughening modifier. For example, when the Shore hardness of the low temperature toughening modifier is less than 53.0 HA, the powder fluidity of the low temperature toughening modifier is deteriorated, and agglomeration is liable to cause the material to be unusable at all. How to greatly improve the hardness and tensile strength of the low temperature toughening modifier under the premise of ensuring the elongation at break of the high PVC low temperature toughening modifier, or to maintain the hardness of the low temperature toughening modifier Under the premise of constant tensile strength, greatly improving the elongation at break of low temperature toughening modifier is the key technology to improve the toughness, ie elongation at break, of PVC products. Under the premise of not affecting the hardness and tensile strength of a polymer material such as PVC as much as possible, the toughness, that is, the elongation at break of the polymer material is improved. However, to date, no researcher has studied the problem of improving the elongation at break of low-temperature toughening modifiers while maintaining the hardness and tensile strength of the low-temperature toughening modifier as much as possible. No researcher has done a great job to improve the toughness, ie, the elongation at break, of the mixture of polymer materials such as PVC, and to give the research results on how to maintain the hardness and tensile strength of PVC products.

Summary of the invention

The first technical problem to be solved by the present invention is to provide a low-temperature toughening modifier for polyvinyl chloride having high hardness, high tensile strength and high elongation at break, and the low-temperature toughening modifier can be substantially Affect PVC Under the premise of hardness and tensile strength, the elongation at break of PVC hard products is greatly improved to solve the problems existing in the prior art.

A second technical problem to be solved by the present invention is to provide a polyvinyl chloride composition which greatly increases the elongation at break without substantially affecting the hardness and tensile strength of PVC.

In order to solve the above first technical problem, the technical solution of the present invention is:

A polyvinyl chloride low temperature toughening modifier, wherein the low temperature toughening modifier is a rubber powder having an elongation at break of 1000 to 1600%, a Shore hardness of >53.0 HA, and a tensile strength of >9.0 MPa.

As a preferred technical solution, the low temperature toughening modifier is selected from the group consisting of chlorinated polyethylene, or a graft copolymer of the chlorinated polyethylene and alkyl (meth) acrylate, or An interpenetrating network copolymer of chlorinated polyethylene and an alkyl (meth)acrylate, or a mixture of the chlorinated polyethylene and an alkyl (meth)acrylate copolymer.

The improvement of the invention is to use a rubber powder with good elongation at break of 1000-1600%, Shore hardness >53.0HA, tensile strength >9.0MPa, and good compatibility with PVC as low temperature toughening modification of PVC. The rubber powder may be one of the above low temperature toughening modifiers as long as it has good compatibility with PVC, for example, the chlorinated polyethylene itself, the chlorinated polyethylene and the (meth)acrylic acid. a graft copolymer of an alkyl ester, an interpenetrating network copolymer of the chlorinated polyethylene and an alkyl (meth)acrylate, or the chlorinated polyethylene and an alkyl (meth)acrylate a mixture of copolymers, and the like. As long as the above-mentioned low temperature toughening modifier has an elongation at break of 1000 to 1600%, a Shore hardness of >53.0 HA, and a tensile strength of >9.0 MPa, the elongation at break of PVC is greatly improved, and The other physical and chemical properties of PVC have a significant impact.

The inventors have confirmed through a large number of theoretical analysis and experimental verification that when the elongation at break of the low temperature toughening modifier is less than 1000%, the toughening effect will decrease; when the elongation at break is greater than 1600%, the reaction kettle The viscosity of the reaction medium is greatly increased, the chlorination reaction rate is too slow, and the production efficiency is drastically lowered. When the Shore hardness is less than 53.0HA, the powder of the low temperature toughening modifier has poor fluidity, is easy to agglomerate, and cannot be uniformly mixed with the PVC powder. At the same time, even if it can be used barely, the hardness of the PVC product is lowered; The tensile strength of the agent must be greater than 9.0 MPa. If it is less than 9.0 MPa, the tensile strength of the PVC product will be significantly affected.

The content of the alkyl (meth)acrylate in the low temperature toughening modifier is from 0 to 50% by weight. The alkyl group of the (meth)acrylic acid ester has from 1 to 12 carbon atoms. The content of the (meth)acrylic acid alkyl ester increases the processability, but the cost is greatly increased. Generally, the lower the content of the (meth) acrylate alkyl ester, the better, if the processability satisfies the requirements.

As a further preferred embodiment, the raw material high-density polyethylene selected for the preparation of the chlorinated polyethylene has a Mn of 2.5 to 65,000, a molecular weight distribution (Mw/Mn) of 4.0, and a particle diameter D _{50 of} 200 μm. The inventors have found that high density polyethylene (HDPE) has an optimum Mn of between 25,000 and 65,000. If Mn is less than 25,000, the molecular weight distribution must be reduced to less than 2.0, which will greatly increase the cost of HDPE. If the molecular weight distribution is more than 2.0 when Mn is less than 25,000, a rubber powder having an elongation at break of more than 1000%, a Shore hardness of more than 53.0 HA, and a tensile strength of more than 9.0 MPa cannot be obtained. If the Mn of the HDPE is more than 65,000, the plasticizing speed of the obtained low-temperature toughening modifier is too slow, the processing property is deteriorated, and a PVC product having good surface properties cannot be obtained. If the molecular weight distribution of HDPE is greater than 4.0, when the elongation at break of the low temperature toughening modifier powder is greater than 1000, the Shore hardness will be less than 53.0 HA, and the tensile strength will be less than 9.0 MPa, so the molecular weight distribution of HDPE must be less than 4.0. If the particle diameter (D ₅₀ ) is more than 200 μm, the chlorination reaction time of HDPE is too long, the production efficiency is too low, and the cost is too high. Therefore, the performance index of HDPE is: Mn is more than 25,000 and less than 65,000; the molecular weight distribution is as narrow as possible, preferably less than 4.0; the smaller the particle diameter D _{50 of} HDPE powder is, preferably less than 200 micrometers.

As an improved technical solution, the chlorinated polyethylene is prepared by adding 0.01 to 0.5 parts by weight of a dispersant, 0.01 to 0.5 parts by weight of an emulsifier to the reactor, and then adding a dispersion medium to make the above three The total amount of the auxiliary raw materials is 250 parts by weight, and 15 to 40 parts by weight of the high-density polyethylene is further added. The temperature of the reaction material is raised to 70-90 ° C under stirring, and 8 to 50 parts by weight of chlorine gas is introduced. The speed of the chlorine gas is maintained at 13 to 23 parts by weight per hour. While the chlorine gas is introduced, the temperature is slowly raised to 135 to 140 ° C for 1 hour in one hour, and the temperature is maintained between 135 and 142 ° C after the chlorine gas is passed. After an hour, it is cooled to 40 ° C or less, and centrifuged and dried to obtain a rubber powder having an elongation at break of 1000 to 1600%, a Shore hardness of >53.0 HA, and a tensile strength of >9.0 MPa.

As another improved technical solution, the graft copolymer of the chlorinated polyethylene and the (meth) acrylate is prepared by adding 0.01 to 0.5 parts by weight of a dispersant, 0.01 to 0.5 in the reactor. Heavy The amount of the initiator and the dispersion medium are such that the total amount of the three auxiliary raw materials is 250 parts by weight, 15 to 40 parts by weight of the chlorinated polyethylene is added, and the temperature of the reaction material is raised to 70 to 90 ° C under stirring. Adding 1 to 40 parts by weight of alkyl (meth)acrylate, maintaining the temperature at 80-85 ° C, reacting for 2 to 5 hours, cooling to 40 ° C or less, centrifuging and drying to obtain an elongation at break of 1000 to 1600% A rubber powder having a Shore hardness of >53.0 HA and a tensile strength of >9.0 MPa.

The dispersant includes a copolymer of an alkyl (meth)acrylate and (meth)acrylic acid.

The emulsifier includes a polyoxyethylene alkyl ether or a polyoxyethylene fatty acid ester.

The dispersion medium is preferably water or an acid, and the acid is preferably hydrochloric acid.

The initiator may be a water-soluble polymerization initiator or an oil-soluble polymerization initiator, such as an inorganic polymerization initiator such as a persulfate, an organic peroxide or an azo compound, which may be used alone or in combination with sulfite. A thiosulfate, a monosubstituted salt (a hydrogen is replaced by a metal), and a formaldehyde-reducing sodium hyposulfite are used together to form an oxidation-reduction system. Preferably, the persulfate may be, for example, sodium persulfate, potassium persulfate, ammonium persulfate or the like. The organic peroxide may be, for example, t-butyl hydroperoxide, benzoyl peroxide or the like.

As a further preferred technical solution, the chlorinated polyethylene has a chlorine content of 10 to 40%; and the low temperature toughness modifier is used for modifying the polyvinyl chloride with respect to 100 parts by weight of the polyvinyl chloride resin. The amount is 1 to 30 parts by weight. The low temperature toughening modifier has an average particle size of from 40 to 450 microns. If the chlorine content of the chlorinated polyethylene is less than 10%, the rubber powder has poor compatibility with PVC, and higher than 40% causes the elongation at break to decrease.

In order to solve the above second technical problem, the technical solution of the present invention is:

A polyvinyl chloride composition containing the following raw parts by weight: (a) 100 parts of a polyvinyl chloride resin; (b) 1 to 30 parts of the low temperature toughening modification (c) 0.5 to 5 parts of a stabilizer; (d) 0 to 50 parts of a filler; (e) 0 to 50 parts of wood powder; (f) 0 to 10 parts of an acrylate polymer; g) 0 to 20 parts of the impact modifier; (h) 0 to 5 parts of the lubricant and (i) 0 to 10 parts of the pigment.

As a preferred technical solution, the polyvinyl chloride resin is a homopolymer containing 80 to 100% by weight of vinyl chloride units and 0 to 20% by weight of other monomer units copolymerizable with polyvinyl chloride or Copolymer. The present invention generally uses a polyvinyl chloride resin having a degree of polymerization of from 600 to 1300.

As a further preferred embodiment, the other monomer copolymerizable with the polyvinyl chloride is selected from one of vinyl acetate, propylene, styrene, alkyl (meth)acrylate or other vinyl monomer or A mixture of two or more.

As a preferred technical solution:

The stabilizer is at least one of an organotin heat stabilizer, a calcium zinc stabilizer, and a lead salt stabilizer;

The filler is at least one of calcium carbonate, talc, and white carbon;

The acrylate-based polymer is a polymer containing an alkyl (meth) acrylate or an alkyl acrylate;

The lubricant is at least one of oxidized polyethylene wax, polyethylene wax, paraffin wax, stearic acid, stearic acid monoglyceride, and calcium stearate;

The pigment is at least one of titanium dioxide, carbon black, ultramarine blue, and an optical brightener;

The impact modifier is a copolymer of alkyl (meth)acrylate, styrene and butadiene.

Due to the adoption of the above technical solutions, the beneficial effects of the present invention are:

The polyvinyl chloride low-temperature toughening modifier of the present invention is a rubber powder having an elongation at break of 1000 to 1600%, a Shore hardness of >53.0 HA, and a tensile strength of >9.0 MPa. The inventors have long been engaged in the research of polyvinyl chloride modifiers and polyvinyl chloride materials. After a large number of theoretical analysis and experimental verification, the elongation at break, Shore hardness and tensile strength of low temperature toughening modifiers have been confirmed. When it is within the above range, it has the best modification effect.

The inventors have also found through extensive experiments that the number average molecular weight (Mn) and molecular weight distribution (Mw/Mn) of HDPE, a raw material of the low temperature toughening modifier, have a great influence on the hardness and tensile strength of the low temperature toughening modifier. . The inventors have found that under the premise of keeping the number average molecular weight Mn of HDPE constant, the molecular weight of HDPE is narrower, and the low temperature toughening modification obtained under the premise of ensuring the elongation at break of the low temperature toughening modifier is the same. The higher the hardness and tensile strength of the agent; at the same time, while maintaining the same molecular weight distribution of HDPE and the same elongation at break of the low temperature toughening modifier, the higher the Mn of HDPE, the lower the toughening modifier The higher the hardness and tensile strength.

The use of the low-temperature toughening modifier of the present invention to modify a polymer material such as polyvinyl chloride greatly improves the elongation at break of a polymer material such as PVC while substantially reducing the hardness and pull of PVC. Stretch strength. The invention fundamentally solves the contradiction between low hardness and tensile strength when the elongation at break of the low temperature toughening modifier is high, and the hardness and tensile strength can be obtained substantially by using the low temperature toughening modifier. Plastic products such as PVC, which are affected and have a large increase in elongation at break, will greatly expand the use of PVC and other plastic products, and improve the industrial competitiveness of plastic products represented by PVC.

detailed description

The invention is further illustrated below in conjunction with specific embodiments. It is to be understood that the examples are not intended to limit the scope of the invention. In addition, it should be understood that various changes and modifications may be made by those skilled in the art in the form of the present invention.

All "parts" and "%" are by weight unless otherwise indicated. It should be particularly appreciated that the invention is not limited to these examples.

The test methods in the following examples and comparative examples are as follows:

The hardness test method is in accordance with the national standard GB/T 2411-2008;

The test method for tensile strength is in accordance with national standard GB/T 1040.1-2006;

Molecular weight test method, molecular weight distribution test method: liquid phase gel chromatography; using LC98-II (RI) type gel liquid chromatograph produced by Beijing Wenfen Analytical Instrument Technology Development Co., Ltd., 5 mg of each sample After being dissolved in 50 ml of chloroform, it was used for detection.

Determination of elongation at break: For low temperature toughening modifiers, in accordance with national standard GB/T 528-2009; for PVC with low temperature toughening modifier added, in accordance with GB/T 1040.1-2006;

Determination of reaction conversion rate: The conversion rate of the reaction is calculated according to the following formula;

The reaction conversion ratio = (weight of the produced rubber powder / amount of the reactant reactant) × 100%; wherein when chlorine is the reactant, the amount of chlorine gas is calculated as one-half of the actual amount added.

Molding temperature of the PVC sheet product: C ₁ = 165 ° C, C ₂ = 175 ° C, C ₃ = 185 ° C.

Die temperature = 185 °C.

Specifications of the extruder: screw: length to diameter ratio (L/D) = 25, compression ratio = 2.5, main engine speed = 60 rpm.

Die: width = 100mm, thickness = 3mm.

Example 1

To a 24 cubic reactor equipped with a stirring paddle, 0.25 parts of a water-soluble methyl methacrylate/acrylic acid copolymer was added as a dispersing agent, and 0.24 parts of polyethylene oxide lauryl ether was added as an emulsifier. Then, water was added so that the total water consumption and all the auxiliary materials were 250 parts, and 30 parts of the number average molecular weight (Mn) was 42,000, the molecular weight distribution (Mw/Mn) was 4.0, and the particle diameter D ₅₀ was 100 μm. High-density polyethylene. After the temperature of the reaction material was raised to 80 ° C under stirring (ie, the primary chlorine temperature; the same below), 18 parts of chlorine gas (ie, the amount of primary chlorine; the same below) was started, and the rate of chlorine gas was kept at 18 parts/ After an hour, the temperature was raised to 135 ° C while passing chlorine gas, and the temperature rise time was 1 hour, and the temperature was raised and the chlorine gas was simultaneously supplied. After the reaction temperature reaches 135 ° C, the temperature is maintained at 135 ° C (ie, the secondary chlorine temperature; the same below), and the remaining 18 parts of chlorine gas (ie, the amount of secondary chlorine; ). Then, the temperature was maintained between 135 and 138 ° C for 3 hours, cooled to below 40 ° C, centrifuged and dried to obtain a rubber powder having an elongation at break of 1140%, a Shore hardness of 53.2 HA, and a tensile strength of 9.1 MPa ( Sample 1). The conversion of the reaction was 99.1%, and the particle size of the powder was 240 μm.

Example 2

Water, 0.1 part of polymethyl methacrylate/acrylic acid copolymer dispersant, 0.05 parts of initiator were added to a 24 cubic reactor equipped with a stirring paddle, so that the total water consumption and all auxiliary materials were 250 parts. Further, 30 parts of Sample 1 were added. After the temperature of the reaction mass was raised to 80 ° C with stirring, 3 parts of butyl acrylate and 3 parts of methyl methacrylate were further added, and the temperature was maintained at 80 to 85 ° C. After reacting for 3 hours, the mixture was cooled to 40 ° C or lower, centrifuged, and dried to obtain a rubber powder having a breaking elongation of 1150%, a Shore hardness of 53.2 HA, and a tensile strength of 9.2 MPa (Sample 2). The conversion of the reaction was 99.3%, and the particle size of the powder was 310 μm.

Example 3

To a 24 cubic reactor equipped with a stirring paddle, 0.25 parts of a methyl methacrylate/acrylic acid copolymer dissolved in water was added as a dispersing agent, and 0.24 parts of polyethylene oxide lauryl ether was added as an emulsifier. water was then added to bring the total water and all auxiliary materials is 250 parts, then 30 parts of Mn of 35000, Mw / Mn of 3.6, a particle size D ₅₀ of 100 microns high density polyethylene. After the temperature of the reaction material was raised to 80 ° C under stirring, 18 parts of chlorine gas was introduced, the rate of chlorine gas was kept at 18 parts / hour, and then the temperature was raised to 135 ° C while passing chlorine gas, and the temperature was raised for 1 hour. Chlorine gas is simultaneously carried out. After the reaction temperature reached 135 ° C, the temperature was maintained at 135 ° C, and the remaining 18 parts of chlorine gas was introduced at a rate of 18 parts per hour. Then, the temperature was maintained between 138 and 142 ° C for 3 hours, and then cooled to 40 ° C or less, and centrifuged and dried to obtain a rubber powder having an elongation at break of 1210%, a Shore hardness of 54.0 HA, and a tensile strength of 9.4 MPa. (Sample 3). The conversion of the reaction was 99.2%, and the particle size of the powder was 340 μm.

Example 4

To a 24 cubic reactor equipped with a stirring paddle, 0.25 parts of a methyl methacrylate/acrylic acid copolymer dissolved in water was added as a dispersing agent, and 0.24 parts of polyethylene oxide lauryl ether was added as an emulsifier. water was then added to bring the total water and all auxiliary materials is 250 parts, then 30 parts of Mn of 2.5, Mw / Mn of 2.4 and a particle diameter D ₅₀ of 100 to 150 micron high density polyethylene. After the temperature of the reaction material was raised to 80 ° C under stirring, 15 parts of chlorine gas was introduced, the rate of chlorine gas was kept at 15 parts / hour, and then the temperature was raised to 135 ° C while passing chlorine gas, and the temperature was raised for 1 hour. Chlorine gas is simultaneously carried out. After the reaction temperature reached 135 ° C, the temperature was maintained at 135 ° C, and the remaining 21 parts of chlorine gas was introduced at a rate of 21 parts per hour. Then, the temperature was maintained at 135 to 138 ° C for 3 hours, and then cooled to 40 ° C or less, centrifuged, and dried to obtain a rubber powder having an elongation at break of 1360%, a Shore hardness of 55 HA, and a tensile strength of 9.3 MPa ( Sample 4). The reaction conversion ratio was 99.1%, and the powder had a particle diameter of 330 μm.

Example 5

To a 30 liter reactor equipped with a stirring paddle, 0.25 parts of a methyl methacrylate/acrylic acid copolymer dissolved in water was added as a dispersing agent, and 0.24 parts of polyethylene oxide lauryl ether was added as an emulsifier. water was then added to bring the total water and all auxiliary materials is 250 parts, then 30 parts of Mn of 62000, Mw / Mn was 3.60, particle diameter D ₅₀ of 100 to 150 micron high density polyethylene. After the temperature of the reaction material was raised to 90 ° C under stirring, 15 parts of chlorine gas was introduced, the rate of chlorine gas was kept at 15 parts / hour, and then the temperature was raised to 140 ° C while passing chlorine gas, and the temperature was raised for 1 hour. Chlorine gas is simultaneously carried out. After the reaction temperature reached 140 ° C, the temperature was maintained at 140 to 143 ° C, and the remaining 21 parts of chlorine gas was introduced at a rate of 21 parts per hour. Then, the temperature was maintained at 140 to 143 ° C for 3 hours, and then cooled to 40 ° C or less, centrifuged, and dried to obtain a rubber powder having an elongation at break of 1550%, a Shore hardness of 57 HA, and a tensile strength of 10.2 MPa ( Sample 5). The conversion of the reaction was 99.1%, and the particle size of the powder was 280 μm.

Example 6

To a 30 liter reactor equipped with a stirring slurry, 0.25 parts of a methyl methacrylate/acrylic acid copolymer dissolved in water was added as a dispersing agent, and 0.24 parts of polyethylene oxide lauryl ether was added as an emulsifier. Water was then added to make the total water consumption and all auxiliary materials 250 parts, and then 25 parts of the sample (5). After the temperature of the reaction material was raised to 80 ° C under stirring, 8 parts of octyl acrylate and 5 parts of butyl methacrylate were added, and the temperature was maintained at 80 to 85 ° C. After 4 hours of reaction, the mixture was cooled to 40 ° C or lower. The mixture was centrifuged and dried to obtain a rubber powder having a breaking elongation of 1450%, a Shore hardness of 56 HA, and a tensile strength of 9.8 MPa (Sample 6). The conversion of the reaction was 99.0%, and the particle size of the powder was 230 μm.

Example 7

In the high-speed mixer, add 100 parts of PVC (S-1000 produced by Qilu Branch of China Petrochemical Corporation, average degree of polymerization is 1000), 9 parts (sample 1), 10 parts of calcium carbonate, and 5 parts of titanium dioxide. 2 parts of methyl tin (18% tin content) heat stabilizer, 1 part calcium stearate, 0.5 part paraffin wax (melting point 60 ° C), 0.5 part polyethylene wax (melting point 110 ° C), Stirring was then turned on and the internal temperature was raised to 120 °C. After cooling, a powdery PVC composition was obtained. The mixture was extruded on an extruder to obtain a PVC sheet product, and tensile strength and elongation at break were evaluated.

Example 8 - Example 12

Example 8 - Example 12 Samples 2 to 6 prepared in the above Example 2 - Example 6 were respectively prepared in the same manner as in Example 7.

Comparative example 1

To a 24 cubic reactor equipped with a stirring paddle, 0.25 parts of a methyl methacrylate/acrylic acid copolymer dissolved in water was added as a dispersing agent, and 0.24 parts of polyethylene oxide lauryl ether was added as an emulsifier. Then, water was added so that the total water consumption and all the auxiliary materials were 250 parts, and 30 parts of high-density polyethylene having a Mn of 42,000 and a Mw/Mn of 4.9 was further added. After the temperature of the reaction material was raised to 70 ° C under stirring, 18 parts of chlorine gas was introduced, the rate of chlorine gas was kept at 18 parts / hour, and then the temperature was raised to 135 ° C while passing chlorine gas, and the temperature was raised for 1 hour. Chlorine gas is simultaneously carried out. After the reaction temperature reaches 135 ° C, The remaining 18 parts of chlorine gas were passed at a rate of 18 parts per hour while maintaining the temperature at 135 °C. Then, the temperature was maintained between 135 and 138 ° C for 3 hours, then cooled to below 40 ° C, centrifuged, and dried to obtain a rubber powder having an elongation at break of 950%, a Shore hardness of 51.2 HA, and a tensile strength of 7.5 MPa. (Comparative sample 1). The conversion of the reaction was 99.1%, and the particle size of the powder was 270 μm.

Subsequently, a powdery PVC composition was prepared using Comparative Sample 1, and the preparation method was the same as in Example 7.

Comparative example 2

To a 24 cubic reactor equipped with a stirring slurry, 0.25 parts of a methyl methacrylate/acrylic acid copolymer dissolved in water was added as a dispersing agent, and 0.24 parts of polyethylene oxide lauryl ether was added as an emulsifier. Then, water was added so that the total water consumption and all the auxiliary materials were 250 parts, and 30 parts of high-density polyethylene having a Mn of 23,000 and a Mw/Mn of 3.5 was further added. After the temperature of the reaction material was raised to 80 ° C under stirring, 20 parts of chlorine gas was introduced, the rate of chlorine gas was kept at 20 parts / hour, and then the temperature was raised to 135 ° C while passing chlorine gas, and the temperature was raised for 1 hour. Chlorine gas is simultaneously carried out. After the reaction temperature reached 135 ° C, the temperature was maintained at 135 ° C, and the remaining 13 parts of chlorine gas was introduced at a rate of 13 parts per hour. Then, the temperature was maintained at 135 to 138 ° C for 3 hours, and then cooled to 40 ° C or less, centrifuged, and dried to obtain a rubber powder having an elongation at break of 840%, a Shore hardness of 49 HA, and a tensile strength of 7.6 MPa ( Compare sample 2). The conversion of the reaction was 99.0%, and the particle size of the powder was 260 μm.

Subsequently, a powdery PVC composition was prepared using Comparative Sample 2 in the same manner as in Example 7.

The experimental results of Examples 7-12 and Comparative Examples 1-2 are shown in Table 1.

Table 1

It can be seen from Table 1 that the larger the Mn of the HDPE at the same molecular weight distribution, the higher the elongation at break of the obtained low-temperature toughening modifier, and the higher the hardness and tensile strength (Example 5 and implementation) In Comparative Example 3, the better the toughness of the modified PVC and the higher the elongation at break, the higher the hardness and the higher the tensile strength; the larger the molecular weight distribution of HDPE is, the lower the obtained Mn is. The smaller the elongation at break of the toughening modifier rubber powder, the lower the elongation at break of the PVC sheet product, and the lower the hardness and tensile strength. That is, in the case of a certain Mn, the narrower the molecular weight distribution of HDPE, the greater the elongation at break of the obtained low-temperature toughening modifier, the higher the hardness, the higher the tensile strength, and the corresponding modified PVC has good toughness. The elongation at break is high and the hardness and tensile strength are substantially unaffected.

Example 13-16

The preparation method of the low temperature toughening modifier rubber powder is exactly the same as that of the embodiment 6. The preparation method of the PVC sheet is exactly the same as that of the embodiment 7, except that the amount of the sample (6) added in the PVC composition is different, and the embodiment 7 is different. The number of additions of the sample 6 in 8, 8, and 10 was 2 parts, 7 parts, 11 parts, and 13 parts, respectively.

Comparative Example 3-5

The preparation method of the low temperature toughening modifier rubber powder is exactly the same as that of the embodiment 6. The preparation method of the PVC sheet is exactly the same as that of the embodiment 7, except that the amount of the sample (sample 6) added in the PVC composition is different, and the comparative example 3 The number of additions in 5 (sample 6) was 0.2 parts, 0.5 parts, and 0.8 parts, respectively.

Comparative Example 6

The preparation method of the low temperature toughening modifier rubber powder is exactly the same as that of the embodiment 6, and the preparation method of the PVC sheet is exactly the same as that of the embodiment 7, except that the amount of the sample (sample 6) added in the PVC composition is different, in the comparative example 6 (Sample 6) The number of parts added was 32 parts.

However, due to the poor processing properties of the PVC composition, it cannot be extruded in an extruder.

Comparative Example 7

The preparation method of Example 7 was used except that the low temperature toughening modifier was not added. The raw material formula is 100 parts PVC, 0 parts low temperature toughening modifier, 10 parts CaCO ₃ , 5 parts TiO ₂ , 2 parts methyl tin, 1 part calcium stearate, 0.5 part paraffin wax (melting point 60 ° C), 0.5 The polyethylene sheet prepared by the preparation of the PVC sheet had an elongation at break of 155%, a Shore hardness of 87.4 HD, and a tensile strength of 44.5 MPa.

The experimental results of Examples 13-16 and Comparative Examples 3-5 are shown in Table 2.

Table 2

It can be seen from Table 2 that the higher the addition amount of the low temperature toughening modifier rubber powder, the greater the elongation at break of PVC. When the addition amount of the low temperature toughening modifier rubber powder is less than 1 part, the elongation at break of the PVC sheet product is less than 160%. Therefore, in order to obtain a PVC product having an elongation at break of more than 160%, the amount of the low temperature toughening modifier should be more than one.

Example 17

To a 24 cubic reactor equipped with a stirring slurry, 0.45 parts of a dispersing agent, 0.1 part of an emulsifier, and a reaction medium were added to make the total weight of the three auxiliary materials 250 parts by weight, and then 18 parts by weight. HDPE having a Mn of 45,000, a molecular weight distribution of 3.0, and a D ₅₀ of 195 μm. The temperature was raised to 75 ° C with stirring, chlorine was passed at a chlorine passing rate of 8 parts per hour for one hour, and the temperature was raised to 136 ° C in one hour. Continue to maintain 8 times per hour chlorine flow rate for one hour, keep the temperature between 136 ~ 140 ° C for three hours, then cool to 40 ° C, centrifuge, and dry to obtain elongation at break of 1340%, Shore hardness of 57HA A low temperature toughening modifier powder having a tensile strength of 9.6 MPa (Sample 7).

The sample 7 was modified with the formulation and method shown in Example 7, and the obtained PVC article had an elongation at break of 196%, a Shore hardness of 86.4 HD, and a tensile strength of 43.3 MPa.

Example 18

To a 24 cubic reactor equipped with a stirring slurry, 0.1 part of a dispersing agent, 0.48 parts of an emulsifier, and a reaction medium were added to make the total weight of the three auxiliary materials 250 parts by weight, and then 18 parts by weight. HDPE having a Mn of 45,000, a molecular weight distribution of 2.6, and a D ₅₀ of 160 μm. The temperature was raised to 75 ° C with stirring, chlorine was passed at a chlorine passing rate of 8 parts by weight per hour for one hour, and the temperature was raised to 136 ° C in one hour. Continue to maintain 8 times per hour chlorine flow rate for one hour, keep the temperature between 136-140 ° C for three hours, then cool to 40 ° C, centrifuge, and dry to obtain elongation at break of 1460%, Shore hardness of 59HA A low temperature toughening modifier powder having a tensile strength of 10.3 MPa (Sample 8).

The sample 8 was modified with the formulation and method shown in Example 7, and the obtained PVC article had an elongation at break of 197%, a Shore hardness of 86.8 HD, and a tensile strength of 43.6 MPa.

Comparative Example 8

To a 24 cubic reactor equipped with a stirring slurry, 0.45 parts of a dispersing agent, 0.5 parts of an emulsifier, and then a reaction medium was added to make the total weight of the three auxiliary materials 250 parts by weight, and then 18 parts by weight. HDPE having a Mn of 23,000, a molecular weight distribution of 2.6, and a D ₅₀ of 185 microns. The temperature was raised to 75 ° C with stirring, chlorine was passed at a chlorine passing rate of 10 parts by weight per hour for one hour, and the temperature was raised to 135 ° C in one hour. Continue to maintain 8 times per hour chlorine flow rate for one hour, keep the temperature between 135-140 ° C for three hours, then cool to 40 ° C, centrifuge, and dry to obtain elongation at break of 1100%, Shore hardness of 47HA A low temperature toughening modifier powder having a tensile strength of 6.5 MPa (Comparative Sample 8).

Comparative Sample 8 The PVC was modified with the formulation and method shown in Example 7, and the obtained PVC article had an elongation at break of 184%, a Shore hardness of 85.1 HD, and a tensile strength of 42.2 MPa.

Comparative Example 9

To a 24 cubic reactor equipped with a stirring slurry, 0.45 parts of a dispersing agent, 0.1 part of an emulsifier, and a reaction medium were added to make the total weight of the three auxiliary materials 250 parts by weight, and then 18 parts by weight. HDPE having a Mn of 68,000, a molecular weight distribution of 3.8, and a D ₅₀ of 195 μm. The temperature was raised to 75 ° C with stirring, chlorine was passed at a chlorine passing rate of 8 parts by weight per hour for one hour, and the temperature was raised to 138 ° C in one hour. Continue to maintain 8 times per hour chlorine flow rate for one hour, keep the temperature between 138-140 ° C for three hours, then cool to 40 ° C, centrifuge, and dry to obtain elongation at break of 1260%, Shore hardness of 60HA A low temperature toughening modifier powder having a tensile strength of 11 MPa (Comparative Sample 9).

Comparative Sample 9 The PVC was modified with the formulation and method shown in Example 7, and the obtained PVC composition was not plasticized well in the extruder, and a PVC sheet could not be obtained.

Comparative Example 10

To a 24 cubic reactor equipped with a stirring slurry, 0.45 parts of a dispersing agent, 0.1 part of an emulsifier, and a reaction medium were added to make the total weight of the three auxiliary materials 250 parts by weight, and then 18 parts by weight. HDPE having a Mn of 40,000, a molecular weight distribution of 4.5, and a D ₅₀ of 185 μm. The temperature was raised to 75 ° C with stirring, chlorine was passed at a chlorine passing rate of 8 parts by weight per hour for one hour, and the temperature was raised to 135 ° C in one hour. Continue to maintain 8 times per hour chlorine flow rate for one hour, keep the temperature between 135-140 ° C for three hours, then cool to 40 ° C, centrifuge, and dry to obtain elongation at break of 1240%, Shore hardness of 51HA A low temperature toughening modifier powder having a tensile strength of 8.2 MPa (Comparative Sample 10).

Comparative Sample 10 The PVC was modified with the formulation and method shown in Example 7, and the obtained PVC sheet had an elongation at break of 192%, a Shore hardness of 85.3 HD, and a tensile strength of 42.1 MPa.

Example 19

To a 24 cubic reactor equipped with a stirring slurry, 0.1 part of a dispersing agent, 0.48 parts of an emulsifier, and a reaction medium were added to make the total weight of the three auxiliary materials 250 parts by weight, and then 18 parts by weight. HDPE having a Mn of 64,000, a molecular weight distribution of 2.6, and a D ₅₀ of 160 μm. The temperature was raised to 75 ° C with stirring, chlorine was passed at a chlorine passing rate of 8 parts by weight per hour for one hour, and the temperature was raised to 140 ° C in one hour. Continue to maintain 8 times per hour chlorine flow rate for one hour, keep the temperature between 140-143 ° C for three hours, then cool to 40 ° C, centrifuge, and dry to obtain elongation at break of 1590%, Shore hardness of 61HA A low temperature toughening modifier powder having a tensile strength of 11.3 MPa (Sample 19).

The sample 19 was modified with the formulation and method shown in Example 7, and the obtained PVC article had an elongation at break of 197%, a Shore hardness of 87.2 HD, and a tensile strength of 44.2 MPa.

Example 20

The polyvinyl chloride composition was modified with the sample 19 prepared in Example 19, and the polyvinyl chloride composition contained the following raw parts by weight: (a) 100 parts of a polyvinyl chloride resin; (b) 12 parts of a sample 19 low temperature toughening modifier; (c) 2 parts of calcium zinc stabilizer; (d) 35 parts of filler talc; (e) 40 parts of wood flour; (f) 1 part containing (methyl a polymer of an alkyl acrylate; (g) 0.5 part of an alkyl (meth) acrylate, a copolymer of styrene and butadiene; (h) 2.5 parts of a lubricant stearic acid and (i) 3 parts of pigment carbon black.

Claims

The invention relates to a low-temperature toughening modifier for polyvinyl chloride, characterized in that the low-temperature toughening modifier is rubber with elongation at break of 1000-1600%, Shore hardness >53.0HA and tensile strength >9.0MPa Powder.
The polyvinyl chloride low temperature toughening modifier according to claim 1, wherein said low temperature toughening modifier is selected from the group consisting of chlorinated polyethylene, or said chlorinated polyethylene and (meth)acrylic acid. a graft copolymer of an alkyl ester or an interpenetrating network copolymer of the chlorinated polyethylene and an alkyl (meth)acrylate, or the chlorinated polyethylene and an alkyl (meth)acrylate a mixture of copolymers.
The polyvinyl chloride low temperature toughening modifier according to claim 2, wherein the low temperature toughening modifier contains 0 to 50% by weight of the alkyl (meth) acrylate. The alkyl group of the (meth)acrylic acid ester has 1 to 12 carbon atoms.
The polyvinyl chloride low-temperature toughening modifier according to claim 2, wherein the raw material high-density polyethylene used in the preparation of the chlorinated polyethylene has a Mn of 2.5 to 65,000 and a molecular weight distribution of <4.0. The particle size D 50 <200 μm.
The polyvinyl chloride low temperature toughening modifier according to claim 4, wherein the chlorinated polyethylene is prepared by the following preparation method:

- adding 0.01 to 0.5 part by weight of a dispersant, 0.01 to 0.5 part by weight of an emulsifier to the reactor, and then adding a dispersion medium so that the total amount of the above three auxiliary materials is 250 parts by weight.

- further adding 15 to 40 parts by weight of the high density polyethylene,

- The temperature of the reaction mass is raised to 70-90 ° C under stirring, and 8 to 50 parts by weight of chlorine gas is introduced, and the rate of chlorine gas is maintained at 13 to 23 parts by weight per hour, while chlorine gas is introduced, and the temperature is slow within 1 hour. Warm up to 135 ~ 140 ° C for 1 hour,

- After the chlorine gas is passed, the temperature is maintained between 135 and 142 ° C for 3 hours.

- Then, it is cooled to 40 ° C or less, centrifuged, and dried to obtain a rubber powder having an elongation at break of 1000 to 1600%, a Shore hardness of >53.0 HA, and a tensile strength of >9.0 MPa.
The polyvinyl chloride low temperature toughening modifier according to claim 5, wherein:

The dispersing agent is a copolymer of an alkyl (meth)acrylate and (meth)acrylic acid;

The emulsifier is a polyoxyethylene alkyl ether or a polyoxyethylene fatty acid ester;

The dispersion medium is water or an acid, and the acid is preferably hydrochloric acid.
The polyvinyl chloride low temperature toughening modifier according to claim 2, wherein the graft copolymer of the chlorinated polyethylene and the (meth) acrylate is prepared by the following preparation method:

- adding 0.01 to 0.5 part by weight of a dispersant, 0.01 to 0.5 part by weight of an initiator, and a dispersion medium to the reactor so that the total amount of the three auxiliary materials is 250 parts by weight.

- adding 15 to 40 parts by weight of the chlorinated polyethylene, and the temperature of the reaction material is raised to 70 to 90 ° C under stirring.

- further adding 1 to 40 parts by weight of an alkyl (meth) acrylate, maintaining the temperature at 80 to 85 ° C,

- After reacting for 2 to 5 hours, the mixture is cooled to 40 ° C or lower, centrifuged, and dried to obtain a rubber powder having a breaking elongation of 1,000 to 1600%, a Shore hardness of >53.0 HA, and a tensile strength of >9.0 MPa.
The polyvinyl chloride low temperature toughening modifier according to claim 7, wherein:

The dispersing agent is a copolymer of an alkyl (meth)acrylate and (meth)acrylic acid;

The dispersion medium is water or an acid, and the acid is preferably hydrochloric acid;

The initiator is a water-soluble polymerization initiator or an oil-soluble polymerization initiator, preferably an inorganic polymerization initiator, an organic peroxide or an azo compound; the inorganic polymerization initiator is preferably a persulfate, The sulfate is preferably sodium persulfate, potassium persulfate and ammonium persulfate; the organic peroxide is t-butyl hydroperoxide or benzoyl peroxide; wherein the initiator is used alone or with sulfite A oxidized-reducing system such as a thiosulfate, a monosubstituted salt, and a sodium formaldehyde sulfoxylate is used together.
The polyvinyl chloride low temperature toughening modifier according to claim 2, wherein the chlorinated polyethylene has a chlorine content of 10 to 40%; and the average particle diameter of the low temperature toughness modifier is 40 to 450 microns.
A method for preparing a polyvinyl chloride low temperature toughening modifier according to claim 1, wherein:

The polyvinyl chloride low temperature toughening modifier is chlorinated polyethylene, and the preparation method comprises:

- adding 0.01 to 0.5 part by weight of a dispersant, 0.01 to 0.5 part by weight of an emulsifier to the reactor, and then adding a dispersion medium so that the total amount of the above three auxiliary materials is 250 parts by weight.

- further adding 15 to 40 parts by weight of the high density polyethylene,

- The temperature of the reaction mass is raised to 70-90 ° C under stirring, and 8 to 50 parts by weight of chlorine gas is introduced, and the rate of chlorine gas is maintained at 13 to 23 parts by weight per hour, while chlorine gas is introduced, and the temperature is slow within 1 hour. Warm up to 135 ~ 140 ° C for 1 hour,

- After the chlorine gas is passed, the temperature is maintained between 135 and 142 ° C for 3 hours.

- Then, it is cooled to 40 ° C or less, centrifuged, and dried to obtain a rubber powder having an elongation at break of 1000 to 1600%, a Shore hardness of >53.0 HA, and a tensile strength of >9.0 MPa.
The method for preparing a polyvinyl chloride low temperature toughening modifier according to claim 10, wherein:

The dispersing agent is a copolymer of an alkyl (meth)acrylate and (meth)acrylic acid;

The emulsifier is a polyoxyethylene alkyl ether or a polyoxyethylene fatty acid ester;

The dispersion medium is water or an acid, and the acid is preferably hydrochloric acid.
The method for preparing a polyvinyl chloride low temperature toughening modifier according to claim 10, wherein:

The high density polyethylene has a Mn of 2.5 to 65,000, a molecular weight distribution of <4.0, and a particle diameter D 50 of <200 μm.
A method for preparing a polyvinyl chloride low temperature toughening modifier according to claim 1, wherein:

The polyvinyl chloride low temperature toughening modifier is a graft copolymer of a chlorinated polyethylene and a (meth) acrylate, and the preparation method comprises:

- adding 0.01 to 0.5 part by weight of a dispersant, 0.01 to 0.5 part by weight of an initiator, and a dispersion medium to the reactor so that the total amount of the three auxiliary materials is 250 parts by weight.

- adding 15 to 40 parts by weight of the chlorinated polyethylene, and the temperature of the reaction material is raised to 70 to 90 ° C under stirring.

- further adding 1 to 40 parts by weight of an alkyl (meth) acrylate, maintaining the temperature at 80 to 85 ° C,

- After reacting for 2 to 5 hours, the mixture is cooled to 40 ° C or lower, centrifuged, and dried to obtain a rubber powder having a breaking elongation of 1,000 to 1600%, a Shore hardness of >53.0 HA, and a tensile strength of >9.0 MPa.
The method for preparing a polyvinyl chloride low temperature toughening modifier according to claim 13, wherein:

The dispersing agent is a copolymer of an alkyl (meth)acrylate and (meth)acrylic acid;

The dispersion medium is water or an acid, and the acid is preferably hydrochloric acid;

The initiator is a water-soluble polymerization initiator or an oil-soluble polymerization initiator, preferably inorganic polymerization. An initiator, an organic peroxide or an azo compound; the inorganic polymerization initiator is preferably a persulfate, and the persulfate is preferably sodium persulfate, potassium persulfate and ammonium persulfate; Tert-butyl hydroperoxide or benzoyl peroxide; wherein the initiator is used alone or together with a sulphur-reduction system such as sulfite, thiosulfate, monosubstituted salt and formaldehyde hydrogen sulfoxylate use.
The method for preparing a polyvinyl chloride low temperature toughening modifier according to claim 13, wherein:

The alkyl group of the (meth)acrylic acid ester has 1 to 12 carbon atoms.
A polyvinyl chloride composition characterized in that the polyvinyl chloride composition contains the following raw parts by weight:

(a) 100 parts of polyvinyl chloride resin;

(b) 1 to 30 parts of the low temperature toughening modifier according to any one of claims 1 to 6;

(c) 0.5 to 5 parts of a stabilizer;

(d) 0 to 50 parts of the filler;

(e) 0 to 50 parts of wood flour;

(f) 0 to 10 parts of an acrylate polymer;

(g) 0 to 20 parts of an impact modifier;

(h) 0 to 5 parts of the lubricant, and

(i) 0 to 10 parts of the pigment.
The polyvinyl chloride composition according to claim 16, wherein said polyvinyl chloride resin contains 80 to 100% by weight of vinyl chloride units and 0 to 20% by weight of copolymerizable with polyvinyl chloride. Homopolymer or copolymer of other monomer units.
The polyvinyl chloride composition according to claim 17, wherein said other monomer copolymerizable with polyvinyl chloride is selected from the group consisting of vinyl acetate, propylene, styrene, alkyl (meth)acrylate or One or a mixture of two or more other vinyl monomers.
The polyvinyl chloride composition of claim 16 wherein:

The stabilizer is at least one of an organotin heat stabilizer, a calcium zinc stabilizer, and a lead salt stabilizer;

The filler is at least one of calcium carbonate, talc, and white carbon;

The acrylate-based polymer is a polymer containing an alkyl (meth) acrylate or an alkyl acrylate;

The lubricant is at least one of oxidized polyethylene wax, polyethylene wax, paraffin wax, stearic acid, stearic acid monoglyceride, and calcium stearate;

The pigment is at least one of titanium dioxide, carbon black, ultramarine blue, and an optical brightener;

The impact modifier is a copolymer of alkyl (meth)acrylate, styrene and butadiene.