Modified impact acr for polyvinyl chloride and method for preparing the same

Abstract

The application discloses a modified impact-resistant ACR for polyvinyl chloride and a preparation method thereof, and relates to the field of impact-resistant modifiers. The raw material composition of the modified impact-resistant ACR comprises methyl methacrylate, butyl acrylate, isooctyl acrylate, glycidyl methacrylate, acrylamide, divinylbenzene, maleic anhydride grafted butyl nitrile rubber, methacrylic acid, an initiator, an emulsifier and a catalyst. The maleic anhydride grafted butyl nitrile rubber is obtained by graft polymerization of maleic anhydride and butyl nitrile rubber; and the emulsifier is obtained by mixing sodium dodecyl sulfate and nonylphenol polyoxyethylene ether. The preparation method of the modified impact-resistant ACR comprises the steps of preparing the maleic anhydride grafted butyl nitrile rubber, preparing a pre-emulsion, emulsion polymerization and obtaining the modified impact-resistant ACR. The modified impact-resistant ACR prepared by the application can effectively enhance the low-temperature notched impact strength and the ultraviolet aging resistance of the polyvinyl chloride.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of impact modifiers, in particular to a modified impact ACR for polyvinyl chloride and a preparation method thereof. BACKGROUND

[0002] As a general-purpose plastic with large output and high cost performance, polyvinyl chloride (PVC) is widely used in fields such as building pipes, household appliance housings, decorative materials, and automotive interiors. However, the presence of a large number of chlorine atoms in the molecular chain structure of PVC leads to reduced molecular chain movement ability at low temperatures, making it prone to brittle fracture and significantly reduced notched impact strength. In addition, under outdoor or ultraviolet light irradiation, the PVC molecular chain is prone to photo-oxidative degradation, resulting in surface yellowing, cracking, and mechanical property degradation, which severely limits its application in low-temperature environments and outdoor scenarios.

[0003] To improve the impact resistance of PVC, the industry generally adopts the technical solution of adding impact modifiers. Among them, acrylate copolymers (ACR) have become one of the mainstream impact modifiers due to their good compatibility with PVC matrix, ability to improve processing fluidity, and non-influence on product transparency. However, existing conventional ACRs have limited effectiveness in improving the low-temperature notched impact strength of PVC, as the ACR elastomer phase is difficult to effectively absorb impact energy under low-temperature conditions. The existing technology with publication number CN118955956B discloses a polyvinyl chloride high-impact modifier and a preparation method thereof. This existing technology mainly focuses on low-temperature impact resistance and impact resistance after sudden heating, but it is prone to mechanical property degradation under outdoor ultraviolet environments, cannot meet the weather resistance requirements, and lacks sufficient stability of basic mechanical properties in low-temperature environments. The existing technology with publication number CN120289728A discloses a PVC acrylate additive and a preparation method thereof. Although this existing technology can enhance ultraviolet aging resistance, it lacks low-temperature impact resistance and ultraviolet aging resistance synergy, and cannot meet the demand for multi-performance synergy improvement by users.

[0004] In summary, although the existing technical solutions have improved the impact modifier for polyvinyl chloride to some extent, they still have the following technical problems: they cannot effectively enhance the low-temperature notched impact strength and ultraviolet aging resistance of polyvinyl chloride. SUMMARY

[0005] To solve the above-mentioned problems in the prior art, the present application provides a modified impact ACR for polyvinyl chloride and a preparation method thereof, and achieves the following invention purposes: preparing a modified impact ACR that can effectively enhance the low-temperature notched impact strength and ultraviolet aging resistance of polyvinyl chloride.

[0006] To achieve the above-mentioned purposes, the technical solutions adopted are as follows:

[0007] A modified impact-resistant ACR for polyvinyl chloride, raw materials comprising, in parts by weight: methyl methacrylate 50-60 parts, butyl acrylate 30-40 parts, isooctyl acrylate 10-15 parts, glycidyl methacrylate 2-5 parts, acrylamide 1-3 parts, divinylbenzene 0.5-1.5 parts, maleic anhydride grafted butyl nitrile rubber 5-8 parts, methacrylic acid 1-2 parts, initiator 0.3-0.8 parts, emulsifier 2-3 parts, catalyst 0.8-1 part.

[0008] The maleic anhydride grafted butyl nitrile rubber is obtained by graft polymerization of maleic anhydride and butyl nitrile rubber.

[0009] The initiator is ammonium persulfate APS.

[0010] The emulsifier is obtained by mixing sodium dodecyl sulfate and nonylphenol polyoxyethylene ether, and the mass ratio of sodium dodecyl sulfate to nonylphenol polyoxyethylene ether is 1:1.5.

[0011] The catalyst is triethylamine.

[0012] The application also provides a preparation method of the modified impact-resistant ACR for polyvinyl chloride, comprising the following steps:

[0013] Step one, preparing maleic anhydride grafted butyl nitrile rubber

[0014] The butyl nitrile rubber is added into toluene, and the mass ratio of butyl nitrile rubber to toluene is 1:(5-8.5), nitrogen protection is carried out, the temperature is raised to 70-80℃, and stirring is carried out for 1-2h, and the stirring speed is 200-300rpm; then the temperature is raised to 90-100℃, maleic anhydride is added, the amount of maleic anhydride is 3-5% of the mass of butyl nitrile rubber, an initiation aid is added, the amount of initiation aid is 1-1.5% of the mass of butyl nitrile rubber, and stirring is continuously carried out for 4-6h under nitrogen atmosphere; after the reaction is completed, the product is poured into excess anhydrous ethanol to precipitate, the solid product is collected after filtration, and then washing with anhydrous ethanol for 3-5 times, and drying at a temperature of 80-90℃ until constant weight, to obtain maleic anhydride grafted butyl nitrile rubber. The initiation aid is benzoyl peroxide.

[0015] Step two, preparing pre-emulsion

[0016] The maleic anhydride grafted butyl nitrile rubber is dissolved in ethyl acetate, and the mass ratio of maleic anhydride grafted butyl nitrile rubber to ethyl acetate is 1:(1-2), to obtain a rubber solution.

[0017] Sodium dodecyl sulfate and nonylphenol polyoxyethylene ether are uniformly mixed according to a mass ratio of 1:1.5 to obtain an emulsifier.

[0018] Dissolve the emulsifier in deionized water, the mass ratio of emulsifier to deionized water is (3-4):100, start stirring, the stirring speed is 300-500 rpm, stir until completely dissolved.

[0019] Add butyl acrylate, isooctyl acrylate, rubber solution, glycidyl methacrylate, acrylamide, divinylbenzene, methacrylic acid, methyl methacrylate in turn, heat to 30-40℃, stir for 30-60 min, the stirring speed is 800-1200 rpm, to obtain a pre-emulsion.

[0020] Step three, emulsion polymerization

[0021] Dissolve the initiator in deionized water to prepare an initiator aqueous solution with a mass fraction of 5-10%; divide the initiator aqueous solution into two parts, the volume ratio of the first part of the initiator aqueous solution to the second part of the initiator aqueous solution is 1:2.

[0022] Divide the pre-emulsion into two parts, the volume ratio of the first part of the pre-emulsion to the second part of the pre-emulsion is 1:4.

[0023] Mix the first part of the pre-emulsion with deionized water, the mass ratio of the first part of the pre-emulsion to deionized water is 1:(1.4-1.6), start stirring, the stirring speed is 200-300 rpm, replace with nitrogen for 30 min; heat to 70-75℃, add the first part of the initiator aqueous solution, continue to heat and stir for 30-60 min. Keep the reaction temperature at 70-75℃, while drop the second part of the pre-emulsion and the second part of the initiator aqueous solution, the drop time is 2-4 h; after the drop is completed, add the catalyst, heat to 85-90℃ for heat aging, heat and stir for 1-2 h, to obtain an ACR emulsion.

[0024] Step four, prepare a modified impact ACR

[0025] Cool the ACR emulsion to 40-50℃, add ammonia water to the reaction system, adjust the pH value of the reaction system to 6-7; then add a demulsifier, the amount of the demulsifier is 10-15% of the mass of the ACR emulsion, stir until the precipitate is completely precipitated. Collect the precipitate by filtration, wash it with deionized water for 3-5 times, then vacuum dry, the temperature is 60-70℃, the vacuum degree is -0.08 MPa, dry to constant weight, crush and pass through an 80-120 mesh sieve, to obtain a modified impact ACR.

[0026] The ammonia water has a mass fraction of 10%; the demulsifier is a calcium chloride aqueous solution with a mass fraction of 5-10%.

[0027] In the present application, the anhydride groups of the maleic anhydride grafted butyl nitrile rubber and the epoxy groups of the glycidyl methacrylate undergo epoxy-anhydride ring-opening reaction to form stable ester bond covalent connection. This chemical reaction can anchor the butyl nitrile rubber segment of the maleic anhydride grafted butyl nitrile rubber on the ACR molecular chain, enhance its bonding force with the matrix, avoid separation due to stress during PVC processing or use, and further improve the toughening efficiency.

[0028] Butyl acrylate / iso-octyl acrylate as the main monomer of the ACR "soft core" constitutes the basic elastic matrix of the ACR itself; the maleic anhydride grafted butyl nitrile rubber is dissolved in ethyl acetate and then added to the pre-emulsion, and the butyl nitrile rubber segment is uniformly dispersed and embedded in the ACR basic elastic matrix to form a "composite toughening phase": the ACR basic elastic matrix provides basic toughness and is responsible for absorbing low-energy impact; the butyl nitrile rubber segment as a high-strength elastic dispersed phase can absorb high-energy impact. The synergistic effect of the two makes the impact resistance of the PVC sample cover a wider stress range, and the room temperature impact strength is further improved, and the low temperature impact strength is improved more significantly.

[0029] The beneficial effects of the present application are as follows:

[0030] (1) The modified impact-resistant ACR for polyvinyl chloride can effectively enhance the notched impact strength of the polyvinyl chloride sample at low temperature. The notched impact strength of the polyvinyl chloride test sample prepared by using the modified impact-resistant ACR as raw material is 41.5-44.7 KJ / m 2 , the tensile strength is 57.8-59.5 MPa, and the bending strength is 71.6-74.7 MPa.

[0031] (2) The modified impact-resistant ACR for polyvinyl chloride can effectively enhance the ultraviolet aging resistance of the polyvinyl chloride sample. After ultraviolet aging for 250 h, the notched impact strength retention rate of the polyvinyl chloride test sample prepared by using the modified impact-resistant ACR as raw material at-15℃ is 94.7-96.2%; after ultraviolet aging for 500 h, the notched impact strength retention rate at-15℃ is 89.2-90.3%. BRIEF DESCRIPTION OF DRAWINGS

[0032] The accompanying drawings are included to provide a further understanding of the present application, and are incorporated herein and constitute a part of the detailed description. It is to be understood that the drawings are provided for purposes of illustration only and not as a definition of the limits of the present application. Figure 1 is the Fourier transform infrared spectrum of the maleic anhydride grafted butyl nitrile rubber.

[0033] In order to make the purpose, technical scheme and advantages of the present application clearer, the embodiments of the present application will be further described in detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present application, and are not used to limit the present application.

[0034] ​Modified impact ACR for polyvinyl chloride and preparation method thereof

[0035] A modified impact ACR for polyvinyl chloride, raw materials are composed of, in parts by weight, methyl methacrylate 50 parts, butyl acrylate 40 parts, isooctyl acrylate 10 parts, glycidyl methacrylate 2 parts, acrylamide 3 parts, divinylbenzene 1.5 parts, maleic anhydride grafted butyl nitrile rubber 5 parts, methacrylic acid 1 part, initiator 0.8 parts, emulsifier 3 parts, catalyst 0.8 parts.

[0036] The initiator is ammonium persulfate APS.

[0037] The catalyst is triethylamine.

[0038] A preparation method of a modified impact ACR for polyvinyl chloride, comprising the following steps:

[0039] Step one, preparation of maleic anhydride grafted butyl nitrile rubber

[0040] The butyl nitrile rubber is added to toluene, the mass ratio of butyl nitrile rubber to toluene is 1:5, nitrogen protection, heating to 70℃, stirring for 2h, stirring speed is 200rpm; then heating to 90℃, adding maleic anhydride, the amount of maleic anhydride is 3% of the mass of butyl nitrile rubber, adding initiation aid, the amount of initiation aid is 1% of the mass of butyl nitrile rubber, continue to stir for 6h under nitrogen atmosphere; after the reaction is completed, pour into excess anhydrous ethanol to precipitate the precipitate, filter after the precipitate is completely precipitated, collect the solid product; wash with anhydrous ethanol for 3 times, then dry, the temperature is 80℃, dry to constant weight, get maleic anhydride grafted butyl nitrile rubber. The acrylonitrile content of the butyl nitrile rubber is 25-30%; the initiation aid is benzoyl peroxide.

[0041] Step two, preparation of pre-emulsion

[0042] The maleic anhydride grafted butyl nitrile rubber is dissolved in ethyl acetate, the mass ratio of maleic anhydride grafted butyl nitrile rubber to ethyl acetate is 1:1, to get rubber solution.

[0043] Mix sodium dodecyl sulfate and nonylphenol polyoxyethylene ether uniformly according to the mass ratio of 1:1.5 to get emulsifier. Dissolve the emulsifier in deionized water, the mass ratio of emulsifier to deionized water is 3:100, start stirring, the speed is 300rpm, stir until completely dissolved. Add butyl acrylate, isooctyl acrylate, rubber solution, glycidyl methacrylate, acrylamide, divinylbenzene, methacrylic acid, methyl methacrylate in turn, heat to 30℃, stir for 60min, the speed is 800rpm, to get pre-emulsion.

[0044] Step three, emulsion polymerization

[0045] The initiator is dissolved in deionized water to prepare an initiator aqueous solution with a mass fraction of 5%; the initiator aqueous solution is divided into two parts, and the volume ratio of the first part of the initiator aqueous solution to the second part of the initiator aqueous solution is 1:2.

[0046] The pre-emulsion is divided into two parts, and the volume ratio of the first part of the pre-emulsion to the second part of the pre-emulsion is 1:4.

[0047] The first part of the pre-emulsion is mixed with deionized water, and the mass ratio of the first part of the pre-emulsion to the deionized water is 1:1.4; stirring is started at a speed of 200 rpm, and nitrogen gas is used for replacement for 30 min; the temperature is raised to 70°C, the first part of the initiator aqueous solution is added, and the temperature is continuously maintained at 70°C for 60 min; the reaction temperature is maintained at 70°C, and the second part of the pre-emulsion and the second part of the initiator aqueous solution are added dropwise, and the dropwise addition time is 4 h; after the dropwise addition is completed, the catalyst is added, the temperature is raised to 85°C for aging, and the temperature is maintained at 85°C for 2 h to obtain an ACR emulsion.

[0048] Step four, a modified impact ACR is prepared

[0049] The ACR emulsion is cooled to 40°C, ammonia water is added dropwise to the reaction system to adjust the pH value of the reaction system to 6; then a demulsifier is added, and the amount of the demulsifier is 10% of the mass of the ACR emulsion; stirring is continued until the precipitation is completely separated out; the separated precipitation is collected by filtration, washed with deionized water for 3 times, and then vacuum dried at a temperature of 60°C and a vacuum degree of -0.08 MPa until the weight is constant; after being crushed and sieved through a 80-120 mesh screen, a modified impact ACR is obtained.

[0050] The ammonia water has a mass fraction of 10%; and the demulsifier is a calcium chloride aqueous solution with a mass fraction of 5-10%.

[0051] Example 2: A modified impact ACR for polyvinyl chloride and a preparation method thereof

[0052] A modified impact ACR for polyvinyl chloride, in parts by weight, has the following raw material composition: methyl methacrylate 55 parts, butyl acrylate 35 parts, isooctyl acrylate 13 parts, glycidyl methacrylate 3 parts, acrylamide 2 parts, divinylbenzene 1 part, maleic anhydride grafted butyl nitrile rubber 6 parts, methacrylic acid 2 parts, initiator 0.5 part, emulsifier 2.5 parts, and catalyst 0.9 part.

[0053] The initiator is ammonium persulfate (APS).

[0054] The catalyst is triethylamine.

[0055] A preparation method of a modified impact ACR for polyvinyl chloride includes the following steps:

[0056] Step one, preparing maleic anhydride grafted butyl nitrile rubber

[0057] The nitrile rubber is added into toluene, the mass ratio of nitrile rubber to toluene is 1:7, nitrogen protection is carried out, the temperature is increased to 75℃, stirring is carried out for 1.5h, the stirring speed is 300rpm; then the temperature is increased to 95℃, maleic anhydride is added, the amount of maleic anhydride is 4% of the mass of nitrile rubber, an initiation aid is added, the amount of initiation aid is 1.5% of the mass of nitrile rubber, the reaction is continuously stirred for 5h under the nitrogen atmosphere; after the reaction is completed, the precipitate is separated out by pouring into excess anhydrous ethanol, the solid product is collected after the complete precipitation is filtered, then the solid product is washed with anhydrous ethanol for 4 times, and then dried, the temperature is 90℃, the drying is carried out until the constant weight, and the maleic anhydride grafted nitrile rubber is obtained. The acrylonitrile content of the nitrile rubber is 25-30%; the initiation aid is benzoyl peroxide.

[0058] Step two, preparation of pre-emulsion

[0059] The maleic anhydride grafted nitrile rubber is dissolved in ethyl acetate, the mass ratio of maleic anhydride grafted nitrile rubber to ethyl acetate is 1:1.5, and a rubber solution is obtained.

[0060] The sodium dodecyl sulfate and nonylphenol polyoxyethylene ether are uniformly mixed according to the mass ratio of 1:1.5, and an emulsifier is obtained.

[0061] The emulsifier is dissolved in deionized water, the mass ratio of emulsifier to deionized water is 3.5:100, stirring is started, the stirring speed is 400rpm, and the stirring is carried out until complete dissolution. Butyl acrylate, isooctyl acrylate, rubber solution, glycidyl methacrylate, acrylamide, divinylbenzene, methacrylic acid and methyl methacrylate are sequentially added, the temperature is increased to 35℃, the stirring is carried out for 60min, the stirring speed is 1000rpm, and a pre-emulsion is obtained.

[0062] Step three, emulsion polymerization

[0063] The initiator is dissolved in deionized water to prepare an initiator aqueous solution with a mass fraction of 8%; the initiator aqueous solution is divided into two parts, and the volume ratio of the first part of initiator aqueous solution to the second part of initiator aqueous solution is 1:2.

[0064] The pre-emulsion is divided into two parts, and the volume ratio of the first part of pre-emulsion to the second part of pre-emulsion is 1:4.

[0065] The first pre-emulsion was mixed with deionized water, the mass ratio of the first pre-emulsion to deionized water was 1:1.5, stirring was started with a speed of 300 rpm, and nitrogen was passed for 30 min; the temperature was raised to 75℃, the first initiator aqueous solution was added, and the temperature was kept for 60 min. The reaction temperature was kept at 75℃, and the second pre-emulsion and the second initiator aqueous solution were added dropwise, the dropwise adding time was 3 h; after the dropwise adding was completed, the catalyst was added, the temperature was raised to 90℃ for aging, the temperature was kept for 2 h, and the ACR emulsion was obtained.

[0066] Step four, the modified impact ACR was prepared

[0067] The ACR emulsion was cooled to 40℃, ammonia was added dropwise to the reaction system to adjust the pH value of the reaction system to 7; then the demulsifier was added, the amount of the demulsifier was 15% of the mass of the ACR emulsion, and the stirring was continued until the precipitation was completely separated out. The separated precipitation was collected by filtration, washed with deionized water for 4 times, then vacuum dried at a temperature of 70℃ and a vacuum degree of -0.08 MPa until the weight was constant, crushed, and then sieved through a 80-120 mesh sieve to obtain the modified impact ACR.

[0068] The ammonia had a mass fraction of 10%; and the demulsifier was a calcium chloride aqueous solution with a mass fraction of 5-10%.

[0069] Example 3: A modified impact ACR for polyvinyl chloride and a preparation method thereof

[0070] A modified impact ACR for polyvinyl chloride, the raw material composition included, by weight: methyl methacrylate 60 parts, butyl acrylate 30 parts, isooctyl acrylate 15 parts, glycidyl methacrylate 5 parts, acrylamide 1 part, divinylbenzene 0.5 part, maleic anhydride grafted butadiene-acrylonitrile rubber 8 parts, methacrylic acid 2 parts, initiator 0.3 part, emulsifier 2 parts, and catalyst 1 part.

[0071] The initiator was ammonium persulfate APS.

[0072] The catalyst was triethylamine.

[0073] A preparation method of a modified impact ACR for polyvinyl chloride, including the following steps:

[0074] Step one, preparing maleic anhydride grafted butadiene-acrylonitrile rubber

[0075] The butyl nitrile rubber is added into toluene, the mass ratio of butyl nitrile rubber to toluene is 1:8.5, nitrogen protection is carried out, the temperature is increased to 80℃, and stirring is carried out for 1h, the stirring speed is 300rpm; then the temperature is increased to 100℃, maleic anhydride is added, the amount of maleic anhydride is 5% of the mass of butyl nitrile rubber, an initiation aid is added, the amount of initiation aid is 1.5% of the mass of butyl nitrile rubber, and the reaction is continuously stirred for 4h under a nitrogen atmosphere; after the reaction is completed, the product is poured into excess anhydrous ethanol to precipitate, the solid product is collected after filtration, and then the solid product is washed with anhydrous ethanol for 5 times and dried at 90℃ until the weight is constant, thereby obtaining the maleic anhydride grafted butyl nitrile rubber. The acrylonitrile content of the butyl nitrile rubber is 25-30%; and the initiation aid is benzoyl peroxide.

[0076] Step two, preparation of pre-emulsion

[0077] The maleic anhydride grafted butyl nitrile rubber is dissolved in ethyl acetate, the mass ratio of maleic anhydride grafted butyl nitrile rubber to ethyl acetate is 1:2, and a rubber solution is obtained.

[0078] Sodium dodecyl sulfate and nonylphenol polyoxyethylene ether are uniformly mixed according to a mass ratio of 1:1.5 to obtain an emulsifier. The emulsifier is dissolved in deionized water according to a mass ratio of 4:100, stirring is started, and the stirring speed is 500rpm until complete dissolution. Butyl acrylate, isooctyl acrylate, the rubber solution, glycidyl methacrylate, acrylamide, divinylbenzene, methacrylic acid, and methyl methacrylate are sequentially added, the temperature is increased to 40℃, and stirring is carried out for 30min at a stirring speed of 1200rpm to obtain a pre-emulsion.

[0079] Step three, emulsion polymerization

[0080] The initiator is dissolved in deionized water to prepare an initiator aqueous solution with a mass fraction of 10%; the initiator aqueous solution is divided into two parts, and the volume ratio of the first part of the initiator aqueous solution to the second part of the initiator aqueous solution is 1:2.

[0081] The pre-emulsion is divided into two parts, and the volume ratio of the first part of the pre-emulsion to the second part of the pre-emulsion is 1:4.

[0082] The first part of the pre-emulsion is mixed with deionized water according to a mass ratio of 1:1.6, stirring is started, the stirring speed is 300rpm, and nitrogen replacement is carried out for 30min; the temperature is increased to 75℃, the first part of the initiator aqueous solution is added, and the temperature is continuously maintained for 30min. The reaction temperature is maintained at 75℃, and the second part of the pre-emulsion and the second part of the initiator aqueous solution are added dropwise, the dropwise adding time is 2h; after the dropwise adding is completed, a catalyst is added, the temperature is increased to 90℃ for temperature maintenance and curing, temperature maintenance and stirring are carried out for 1h, and an ACR emulsion is obtained.

[0083] Step four, modified impact ACR is prepared

[0084] The ACR emulsion is cooled to 50°C, ammonia is added dropwise to the reaction system, and the pH of the reaction system is adjusted to 7; then a demulsifier is added, the amount of demulsifier is 15% of the mass of the ACR emulsion, and stirring is performed until the precipitate is completely separated. The separated precipitate is collected by filtration, washed with deionized water 5 times, then vacuum dried at a temperature of 70°C and a vacuum degree of -0.08 MPa, dried to a constant weight, crushed and sieved through an 80-120 mesh sieve to obtain the modified impact ACR.

[0085] The ammonia has a mass fraction of 10%; the demulsifier is a calcium chloride aqueous solution with a mass fraction of 5-10%.

[0086] Comparative example 1

[0087] An impact ACR for polyvinyl chloride, the raw material composition is: 55 parts of methyl methacrylate, 35 parts of butyl acrylate, 13 parts of isooctyl acrylate, 3 parts of glycidyl methacrylate, 2 parts of acrylamide, 1 part of divinylbenzene, 2 parts of methacrylic acid, 0.5 parts of initiator, 2.5 parts of emulsifier, and 0.9 parts of catalyst.

[0088] The initiator is ammonium persulfate APS.

[0089] The catalyst is triethylamine.

[0090] A preparation method of an impact ACR for polyvinyl chloride, comprising the following steps:

[0091] Step one, preparation of pre-emulsion

[0092] Sodium dodecyl sulfate and nonylphenol polyoxyethylene ether are uniformly mixed according to a mass ratio of 1:1.5 to obtain an emulsifier.

[0093] The emulsifier is dissolved in deionized water, the mass ratio of emulsifier to deionized water is 3.5:100, stirring is started with a speed of 400 rpm until complete dissolution. Methyl methacrylate, butyl acrylate, isooctyl acrylate, glycidyl methacrylate, acrylamide, and divinylbenzene are added in sequence, the temperature is raised to 35°C, and stirring is performed for 60 min at a speed of 1000 rpm to obtain a pre-emulsion.

[0094] Step two, emulsion polymerization

[0095] This step is the same as the "emulsion polymerization" step in example 2.

[0096] Step three, impact ACR is prepared

[0097] This step is the same as the "modified impact ACR is prepared" step in example 2.

[0098] Comparative Example 2

[0099] An impact-resistant ACR for polyvinyl chloride, the raw material composition in parts by weight: methyl methacrylate 55 parts, butyl acrylate 35 parts, isooctyl acrylate 13 parts, acrylamide 2 parts, divinylbenzene 1 part, maleic anhydride grafted butadiene-acrylonitrile rubber 6 parts, methacrylic acid 2 parts, initiator 0.5 parts, emulsifier 2.5 parts, catalyst 0.9 parts.

[0100] The initiator is ammonium persulfate APS.

[0101] The catalyst is triethylamine.

[0102] A preparation method of an impact-resistant ACR for polyvinyl chloride, comprising the following steps:

[0103] Step one, preparation of maleic anhydride grafted butadiene-acrylonitrile rubber

[0104] This step is the same as the "preparation of maleic anhydride grafted butadiene-acrylonitrile rubber" step in Example 2.

[0105] Step two, preparation of pre-emulsion

[0106] Dissolve the maleic anhydride grafted butadiene-acrylonitrile rubber in ethyl acetate, the mass ratio of maleic anhydride grafted butadiene-acrylonitrile rubber to ethyl acetate is 1:1.5, and a rubber solution is obtained.

[0107] Mix sodium dodecyl sulfate and nonylphenol polyoxyethylene ether uniformly according to a mass ratio of 1:1.5 to obtain an emulsifier.

[0108] Dissolve the emulsifier in deionized water, the mass ratio of emulsifier to deionized water is 3.5:100, start stirring at a speed of 400 rpm, and stir until completely dissolved. Add methyl methacrylate, butyl acrylate, isooctyl acrylate, acrylamide, divinylbenzene, and the rubber solution in sequence, heat to 35°C, stir for 60 min at a speed of 1000 rpm, and obtain a pre-emulsion.

[0109] Step three, emulsion polymerization

[0110] This step is the same as the "emulsion polymerization" step in Example 2.

[0111] Step four, preparation of impact-resistant ACR

[0112] This step is the same as the "preparation of modified impact-resistant ACR" step in Example 2.

[0113] Example 4 Performance test

[0114] The preparation method of the test sample is as follows: the raw materials are weighed and proportioned as follows: 100 parts of PVC resin, 10 parts of impact ACR, 5 parts of calcium-zinc stabilizer, and 2 parts of lubricant; melt blending in a double-screw extruder, the screw rotation speed is 300 rpm, the temperature is 160-185 DEG C, and then injection molding after extruding and granulating to obtain the polyvinyl chloride test sample.

[0115] The calcium-zinc stabilizer is a special composite calcium-zinc stabilizer for polyvinyl chloride, and the molar ratio of calcium stearate to zinc stearate is 1.5:1; the lubricant is obtained by mixing butyl stearate and polyethylene wax, and the mass ratio of butyl stearate to polyethylene wax is 3:2.

[0116] (I) The impact ACR prepared in Examples 1-3 and Comparative Examples 1-2 is used as raw material to prepare polyvinyl chloride test samples, and the notched impact strength at-15 DEG C is tested according to the test method specified in GB / T 1043.1-2008, the tensile strength is tested according to the test method specified in GB / T 1040-2018, and the bending strength is tested according to the test method specified in GB / T 9341-2008. The specific test results are shown in Table 1.

[0117] Table 1

[0118]

[0119] As shown in Table 1, the notched impact strength of the polyvinyl chloride test sample prepared by using the modified impact ACR prepared in Examples 1-3 as raw material is 41.5-44.7 KJ / m 2 , the tensile strength is 57.8-59.5 MPa, and the bending strength is 71.6-74.7 MPa. It is proved that the modified impact ACR prepared by the present application can effectively enhance the notched impact strength of the polyvinyl chloride sample at low temperature, and also maintains good tensile strength and bending strength.

[0120] (II) The impact ACR prepared in Examples 1-3 and Comparative Examples 1-2 is used as raw material to prepare polyvinyl chloride test samples, and the anti-ultraviolet aging test is carried out according to the test method specified in GB / T 16422.3-2014. The anti-ultraviolet aging test method is as follows: the polyvinyl chloride test sample is placed in an ultraviolet aging test box, and the notched impact strength retention rate (%) at-15 DEG C after 250h and 500h of cyclic aging is calculated, the cycle is 8h of irradiation exposure at black standard temperature 60 DEG C, and then 4h of condensation exposure at black standard temperature 50 DEG C. The specific test results are shown in Table 2.

[0121] Table 2

[0122]

[0123] As shown in the test results in Table 2, the modified impact-resistant ACR prepared in Examples 1-3 is used as a raw material to prepare a polyvinyl chloride test sample, after UV aging for 250 h, the notched impact strength retention at -15℃ is 94.7-96.2%, after UV aging for 500 h, the notched impact strength retention at -15℃ is 89.2-90.3%. It is proved that the modified impact-resistant ACR prepared in the application can effectively enhance the anti-UV aging performance of the polyvinyl chloride sample.

[0124] Obviously, there are still many specific implementation methods that can be changed under the concept of the application, and here it should be declared that any changes made under the inventive concept of the application will fall within the scope of protection of the application.

Claims

1. A modified impact ACR for polyvinyl chloride, characterized by: The raw material composition of the modified impact ACR comprises methyl methacrylate, butyl acrylate, isooctyl acrylate, glycidyl methacrylate, acrylamide, divinylbenzene, maleic anhydride grafted butyl nitrile rubber, methacrylic acid, initiator, emulsifier, catalyst; The initiator is ammonium persulfate APS; the emulsifier is obtained by mixing sodium dodecyl sulfate and nonylphenol polyoxyethylene ether; and the catalyst is triethylamine; The preparation method of the impact ACR comprises the steps of preparing maleic anhydride grafted butyl nitrile rubber, preparing pre-emulsion, emulsion polymerization, and obtaining modified impact ACR. The pre-emulsion preparation comprises the following steps: dissolving the emulsifier in deionized water, the mass ratio of the emulsifier to the deionized water being (3-4):100; sequentially adding butyl acrylate, isooctyl acrylate, a rubber solution, glycidyl methacrylate, acrylamide, divinylbenzene, methacrylic acid, and methyl methacrylate, heating to 30-40℃, and stirring for 30-60 min to obtain the pre-emulsion; the rubber solution is obtained by dissolving the maleic anhydride grafted butyl nitrile rubber in ethyl acetate, the mass ratio of the maleic anhydride grafted butyl nitrile rubber to the ethyl acetate being 1:(1-2); The emulsion polymerization is carried out at a reaction temperature of 70-75℃ and a curing temperature of 80-85℃. The modified impact ACR is obtained by cooling the ACR emulsion obtained after the emulsion polymerization to 40-50℃, adjusting the pH value of the reaction system to 6-7, and then adding a demulsifier and stirring until the precipitation is completely separated out.

2. The modified impact ACR for polyvinyl chloride according to claim 1, characterized in that: The raw material weight composition of the modified impact ACR comprises 50-60 parts of methyl methacrylate, 30-40 parts of butyl acrylate, 10-15 parts of isooctyl acrylate, 2-5 parts of glycidyl methacrylate, 1-3 parts of acrylamide, 0.5-1.5 parts of divinylbenzene, 5-8 parts of maleic anhydride grafted butyl nitrile rubber, 1-2 parts of methacrylic acid, 0.3-0.8 parts of initiator, 2-3 parts of emulsifier, and 0.8-1 part of catalyst.

3. The process for the preparation of modified impact ACR for PVC as claimed in claim 1, wherein: The maleic anhydride grafted butyl nitrile rubber is prepared by the following steps: adding butyl nitrile rubber into toluene, protecting under nitrogen atmosphere, heating to 70-80℃, and stirring for 1-2 h; then heating to 90-100℃, adding maleic anhydride and an initiating aid, and continuing to stir for 4-6 h under nitrogen atmosphere.

4. The process for preparing modified impact ACR for polyvinyl chloride as claimed in claim 1, wherein: The mass ratio of the butyl nitrile rubber to toluene is 1:(5-8.5); The amount of the maleic anhydride is 3-5% of the mass of the butyl nitrile rubber.

5. The process for preparing modified impact ACR for PVC as claimed in claim 1, wherein: The initiating aid is benzoyl peroxide, and the amount of the initiating aid is 1-1.5% of the mass of the butyl nitrile rubber.

6. The process for preparing modified impact ACR for polyvinyl chloride as claimed in claim 1, wherein: The demulsifier is a calcium chloride aqueous solution with a mass fraction of 5-10%, and the amount of the demulsifier is 10-15% of the mass of the ACR emulsion.

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