CN114292478A - Preparation method of modified material for PVC - Google Patents
Preparation method of modified material for PVC Download PDFInfo
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- CN114292478A CN114292478A CN202210181775.8A CN202210181775A CN114292478A CN 114292478 A CN114292478 A CN 114292478A CN 202210181775 A CN202210181775 A CN 202210181775A CN 114292478 A CN114292478 A CN 114292478A
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Abstract
The invention discloses a preparation method of a modified material for PVC, which comprises the following steps: s1 pairs of nano SiO2Carrying out surface treatment; s2 preparing seed emulsion; s3, preparing a core-shell modification auxiliary agent, adding the seed latex obtained in the step S2 into a condensation reflux device, heating in a water bath to 73 ℃, adding a certain amount of a core layer initiator and a crosslinking agent, supplementing a certain amount of an emulsifier, slowly adding a core layer monomer, carrying out heat preservation reaction for 1 hour, then adding a shell layer initiator, slowly adding a shell layer monomer, continuously carrying out heat preservation reaction for 1-2 hours, cooling to room temperature, adding a saturated saline solution for demulsification, and carrying out low-temperature vacuum drying to obtain the core-shell modification auxiliary agent. The invention adopts the inorganic nano silicon oxide with surface modification to synthesize the novel impact modifier with the core-shell structure through seed emulsion polymerization, which not only can improve the toughness and the strength of PVC, but also has the advantages of aging resistance and processing improvementThe function of the performance.
Description
Technical Field
The invention belongs to the field of plastic processing aids, and particularly relates to a preparation method of a modified material for PVC.
Background
Polyvinyl chloride (PVC) is one of the well-known, widely used, high-volume, versatile plastic varieties. The polyvinyl chloride has wide sources, simple synthesis method and very reasonable price, and the prepared product has good processing performance and mechanical performance, good chemical stability and excellent flame retardant property, so the polyvinyl chloride has very wide application scenes and very rapid development.
ACR is used as an excellent impact modifier and is widely applied to the PVC industry, but the cost is higher and the domestic production gap is large. Therefore, accelerating the research and development of the ACR modifier is a very urgent task in the PVC industry.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a modified material for PVC, which adopts inorganic nano-silica with surface modification to synthesize a novel impact modifier with a core-shell structure through seeded emulsion polymerization, and not only can improve the toughness and the strength of PVC, but also has the functions of ageing resistance and improving the processing performance.
The invention mainly adopts the technical scheme that:
a preparation method of a modified material for PVC comprises the following specific steps:
s1: to nano SiO2Surface treatment
Mixing nano SiO2Adding the powder into a surfactant diluted alcohol aqueous solution, fully mixing and stirring for 30min, and drying in vacuum to obtain the modified nano SiO2；
S2: preparing seed emulsion
A certain amount of the modified nano SiO obtained in the step S12Dispersing in deionized water, performing ultrasonic dispersion and mechanical stirring for pre-dispersion for 30-40min, adding a certain amount of emulsifier for dispersion for 10-20min, adjusting pH to 9-10 with 5% sodium hydroxide solution, and performing ultrasonic high-speed stirring and dispersion for 30-40min to obtain seed latex;
s3: preparation of core-shell modified auxiliary
And (4) adding the seed latex obtained in the step S2 into a condensation reflux device, heating in a water bath to 73 ℃, adding a certain amount of a nuclear layer initiator and a crosslinking agent, supplementing a certain amount of an emulsifier, slowly adding a nuclear layer monomer, carrying out heat preservation reaction for 1 hour, then adding a shell layer initiator, slowly adding a shell layer monomer, continuing to carry out heat preservation reaction for 1-2 hours, cooling to room temperature, adding a saturated saline solution for demulsification, and carrying out low-temperature vacuum drying to obtain the core-shell modification aid.
Preferably, the surfactant in step S1 is a silane coupling agent, and the amount of the silane coupling agent is SiO20.5-1.0% of the mass.
Preferably, the silane coupling agent is one of butadienyltriethoxysilane, vinyltributyl peroxide silane, dimethoxymethylvinylsilane, gamma- (methacryl) propyltrimethoxysilane, or aminopropyltriethoxysilane.
Preferably, the preparation method of the surfactant diluted alcohol aqueous solution is as follows: weighing a certain amount of surfactant, adding the surfactant into an alcohol-water diluent, uniformly mixing and dispersing, then adjusting the pH value to 3-4, fully stirring for 1-2h, and then adjusting the pH value to 9-10 by using ammonia water to obtain a surfactant diluted alcohol-water solution, wherein the volume ratio of ethanol to water in the alcohol-water diluent is 1:9, and the mass concentration of the surfactant is 0.5-3.5%.
Preferably, in the step S2, the nano SiO is modified2The mass ratio of the emulsifier to the deionized water is 3-6:100, and the addition amount of the emulsifier is nano SiO25-10% of the mass.
Preferably, in the step S3, the core layer monomer is n-butyl acrylate or hexyl acrylate, and the addition amount of the core layer monomer is nano SiO in the seed latex2The mass is 3-4 times, the shell layer monomer is methyl methacrylate, and the shell layer monomer is nano SiO in seed latex21.5-3 times of the mass.
Preferably, the core layer initiator and the shell layer initiator in S3 are one of potassium persulfate, sodium persulfate or ammonium persulfate, the amount of the core layer initiator is 4% of the mass of the core layer monomer, and the amount of the shell layer initiator is 4% of the mass of the shell layer monomer.
Preferably, the cross-linking agent is one of 1, 4-butanediol diacrylate, allyl methacrylate or polyethylene glycol dimethacrylate, and the amount of the cross-linking agent is 1% of the mass of the core layer monomer.
Preferably, the emulsifier is one of sodium dodecyl benzene sulfonate, polyoxyethylene octyl phenol ether-10 or sodium hexadecyl sulfonate.
Preferably, the amount of the emulsifier supplemented when the core layer is prepared in the step S3 is 1.5-3% of the mass of the core layer monomer.
Has the advantages that: the invention provides a preparation method of a modified material for PVC, which has the following advantages:
(1) due to the nanometer SiO2The surface has hydroxyl groups, adjacent hydroxyl groups are combined with each other through hydrogen bonds, hydrogen atoms of isolated hydroxyl groups have strong positive electricity and are easy to adsorb with electronegative atoms, and a coating structure is formed with the silane coupling agent, so that the compatibility with the core layer monomer is increased.
(2) Coated with nano SiO2The silane coupling agent on the surface can react with the core layer monomer under the combined action of the initiator and the cross-linking agent, so that the core layer monomer and the nano SiO2The bonding interface of (A) is a chemical bond bonding, and the reinforcing performance of the filler is obviously improved.
(3) In addition, the shell monomer forms a hard shell on the surface of the core layer monomer through a chemical bond structure, so that the reinforcing property of the modifier is further improved, and the nano SiO in the modifier is based on the inorganic rigid particle toughening theory2The particles are used as stress supporting points to generate a toughening phenomenon, so that the impact resistance of the PVC resin is improved.
Detailed Description
In order to make those skilled in the art better understand the technical solutions in the present application, the technical solutions in the embodiments of the present application are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Example 1
The preparation method of the modified material for PVC comprises the following specific steps:
s1: to nano SiO2Surface treatment
Mixing nano SiO2Powder addition to silane coupling agent (butadienyltriethoxysilane, 1.0% Nano SiO2) Fully mixing and stirring the mixture in a dilute alcohol aqueous solution for 30min, and then drying the mixture in vacuum to obtain modified nano SiO2；
S2: preparing seed emulsion
A certain amount of nano SiO2Dispersed in deionized water (nanometer SiO)2The mass ratio of the deionized water to the deionized water is 3: 100) pre-dispersing for 35min by ultrasonic dispersion and mechanical stirring, and adding emulsifier (sodium dodecyl benzene sulfonate, 5% nanometer SiO)2) After dispersing for 15min, adjusting the pH value to 9-10 by using a 5% sodium hydroxide solution, and carrying out ultrasonic high-speed stirring and redispersion for 30-40min to obtain seed latex;
s3: preparation of core-shell modified auxiliary
Adding the seed latex obtained in the step S2 into a condensation reflux device, heating in a water bath to 73 ℃, adding a core layer initiator (potassium persulfate, 4% of n-butyl acrylate) and a crosslinking agent (1, 4-butanediol diacrylate, 1% of n-butyl acrylate), supplementing an emulsifier (sodium dodecyl benzene sulfonate, 1.5% of n-butyl acrylate), and slowly adding a core layer monomer (n-butyl acrylate, wherein the dosage of the n-butyl acrylate is nano SiO in the seed latex)23 times of the mass), reacting for 1 hour in a heat preservation way, then adding a shell initiator (potassium persulfate, 4 percent of methyl methacrylate), and slowly adding a shell monomer (methyl methacrylate, the dosage of which is nano SiO in the seed latex)21.5 times of the mass), continuously preserving the heat for 1.5 hours, cooling to room temperature, adding a saturated saline solution for demulsification, and performing low-temperature vacuum drying to obtain the core-shell modification auxiliary agent.
Example 2
The preparation method of the modified material for PVC comprises the following specific steps:
s1: to nano SiO2Surface treatment
Mixing nano SiO2Powder addition to silane coupling agent (butadienyltriethoxysilane, 0.5% nano SiO)2) Fully mixing and stirring the mixture in a dilute alcohol aqueous solution for 30min, and then drying the mixture in vacuum to obtain modified nano SiO2；
S2: preparing seed emulsion
A certain amount of nano SiO2Dispersed in deionized water (nanometer SiO)2The mass ratio of the deionized water to the deionized water is 6: 100) pre-dispersing for 35min by ultrasonic dispersion and mechanical stirring, and adding emulsifier (sodium dodecyl benzene sulfonate, 5% nanometer SiO)2) After dispersing for 15min, adjusting the pH value to 9-10 by using a 5% sodium hydroxide solution, and carrying out ultrasonic high-speed stirring and redispersion for 30-40min to obtain seed latex;
s3: preparation of core-shell modified auxiliary
Adding the seed latex obtained in the step S2 into a condensation reflux device, heating in a water bath to 73 ℃, adding a core layer initiator (potassium persulfate, 4% of n-butyl acrylate) and a crosslinking agent (1, 4-butanediol diacrylate, 1% of n-butyl acrylate), supplementing an emulsifier (sodium dodecyl benzene sulfonate, 2% of n-butyl acrylate), and slowly adding a core layer monomer (n-butyl acrylate, wherein the dosage of the n-butyl acrylate is nano SiO in the seed latex23 times of the mass), reacting for 1 hour in a heat preservation way, then adding a shell initiator (potassium persulfate, 4 percent of methyl methacrylate), and slowly adding a shell monomer (methyl methacrylate, the dosage of which is nano SiO in the seed latex)21.5 times of the mass), continuously preserving the heat for 1.5 hours, cooling to room temperature, adding a saturated saline solution for demulsification, and performing low-temperature vacuum drying to obtain the core-shell modification auxiliary agent.
Example 3
The preparation method of the modified material for PVC comprises the following specific steps:
s1: to nano SiO2Surface treatment
Mixing nano SiO2Powder addition to silane coupling agent (butadienyltriethoxysilane, 1% Nano SiO)2) Fully mixing and stirring the mixture in a dilute alcohol aqueous solution for 30min, and then drying the mixture in vacuum to obtain modified nano SiO2；
S2: preparing seed emulsion
A certain amount of nano SiO2Dispersed in deionized water (nanometer SiO)2The mass ratio of the deionized water to the deionized water is 6: 100) pre-dispersing for 35min by ultrasonic dispersion and mechanical stirring, and adding emulsifier (sodium dodecyl benzene sulfonate, 5% nanometer SiO)2) After dispersing for 15min, adjusting the pH value to 9-10 by using a 5% sodium hydroxide solution, and carrying out ultrasonic high-speed stirring and redispersion for 30-40min to obtain seed latex;
s3: preparation of core-shell modified auxiliary
Adding the seed latex obtained in the step S2 into a condensation reflux device, heating in water bath to 73 ℃, adding a nuclear layer initiator (potassium persulfate, 4% n-butyl acrylate) and a crosslinking agent (1, 4-butanediol diacrylate, 1% n-butyl acrylate)Butyl ester), and adding emulsifier (sodium dodecyl benzene sulfonate, 2% n-butyl acrylate), slowly adding core layer monomer (n-butyl acrylate, the amount of nano SiO in seed latex)24 times of the mass), reacting for 1 hour in a heat preservation way, then adding a shell initiator (potassium persulfate, 4 percent of methyl methacrylate), and slowly adding a shell monomer (methyl methacrylate, the dosage of which is nano SiO in the seed latex)23 times of the mass), continuously preserving the heat for 1.5h, cooling to room temperature, adding a saturated saline solution for demulsification, and performing low-temperature vacuum drying to obtain the core-shell modification auxiliary agent.
The method for preparing the surfactant diluted alcohol aqueous solution in examples 1 to 3 was as follows: weighing a certain amount of surfactant, adding the surfactant into an alcohol-water diluent, uniformly mixing and dispersing, then adjusting the pH value to 3-4, fully stirring for 1-2h, and then adjusting the pH value to 9-10 by using ammonia water to obtain a surfactant diluted alcohol-water solution, wherein the volume ratio of ethanol to water in the alcohol-water diluent is 1:9, and the mass concentration of the surfactant is 2.5%.
Test samples were prepared according to the formulations shown in table 1 using the modification aids obtained in examples 1, 2 and 3 and ACR-401, respectively, to obtain sample 1, sample 2, sample 3 and sample 4, respectively.
Table 1: the addition amount of each component in the mixing formula
The mechanical property and the processability of the samples are respectively tested according to a standard test method, and the specific test results are shown in table 2:
from the above table the following conclusions can be drawn:
(1) the impact and tensile properties of samples 1-3 are significantly better than those of sample 4, since on the one hand the nano-silica dispersed in the PVC matrix corresponds to individual physical cross-linking points, and the PVC molecules are connected in some way between these "points" and "dots". These inorganic particles can act as a polydisperse load when the sample is subjected to a tensile force. If one chain is broken, the other chains can still act, so that the whole chain cannot be damaged, and the tensile strength is improved; on the other hand, after the surfaces of the inorganic particles are coated with the acrylate copolymer with the core-shell structure, the compatibility with PVC is increased, the interface bonding is enhanced, so that the stress can be better transferred to the inorganic particles, and the mechanism of toughening the plastic by rubber and the mechanism of toughening the plastic by organic rigid particles and inorganic rigid particles are followed.
(2) The PVC plasticizing time with the addition of samples 1-3 was shortened because of the nano-SiO2Has certain plasticizing synergy with the acrylate copolymer, thereby improving the plasticizing efficiency.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a modified material for PVC is characterized by comprising the following specific steps:
s1: to nano SiO2Surface treatment
Mixing nano SiO2Adding the powder into a surfactant diluted alcohol aqueous solution, fully mixing and stirring for 30min, and drying in vacuum to obtain the modified nano SiO2；
S2: preparing seed emulsion
A certain amount of nano SiO2Dispersing in deionized water, performing ultrasonic dispersion and mechanical stirring for pre-dispersion for 30-40min, adding a certain amount of emulsifier for dispersion for 10-20min, adjusting pH to 9-10 with 5% sodium hydroxide solution, and performing ultrasonic high-speed stirring and dispersion for 30-40min to obtain seed latex;
s3: preparation of core-shell modified auxiliary
And (4) adding the seed latex obtained in the step S2 into a condensation reflux device, heating in a water bath to 73 ℃, adding a certain amount of a nuclear layer initiator and a crosslinking agent, supplementing a certain amount of an emulsifier, slowly adding a nuclear layer monomer, carrying out heat preservation reaction for 1 hour, then adding a shell layer initiator, slowly adding a shell layer monomer, continuing to carry out heat preservation reaction for 1-2 hours, cooling to room temperature, adding a saturated saline solution for demulsification, and carrying out low-temperature vacuum drying to obtain the core-shell modification aid.
2. The method of claim 1, wherein the surfactant in step S1 is a silane coupling agent, and the silane coupling agent is SiO20.5-1.0% of the mass.
3. The method of claim 1, wherein the silane coupling agent is one of butadienyltriethoxysilane, vinyltributylsilane, dimethoxymethylvinylsilane, gamma- (methacryl) propyltrimethoxysilane, or aminopropyltriethoxysilane.
4. The method for preparing a modified material for PVC according to claim 1, wherein the surfactant diluted alcohol aqueous solution is prepared by the following method: weighing a certain amount of surfactant, adding the surfactant into an alcohol-water diluent, uniformly mixing and dispersing, then adjusting the pH value to 3-4, fully stirring for 1-2h, and then adjusting the pH value to 9-10 by using ammonia water to obtain a surfactant diluted alcohol-water solution, wherein the volume ratio of ethanol to water in the alcohol-water diluent is 1:9, and the mass concentration of the surfactant is 0.5-3.5%.
5. The method of claim 1, wherein in the step S2, the nano SiO is added2The mass ratio of the deionized water to the deionized water is 3-6:100, the addition amount of the emulsifier is nano SiO25-10% of the mass.
6. The method of claim 1, wherein in the step S3, the core layer monomer is propyleneN-butyl acrylate or hexyl acrylate, wherein the addition amount of the core layer monomer is nano SiO in the seed latex2The mass is 3-4 times, the shell layer monomer is methyl methacrylate, and the shell layer monomer is nano SiO in seed latex21.5-3 times of the mass.
7. The method for preparing the modified material for PVC according to claim 1, wherein the core layer initiator and the shell layer initiator in S3 are one of potassium persulfate, sodium persulfate or ammonium persulfate, the amount of the core layer initiator is 4% of the mass of the core layer monomer, and the amount of the shell layer initiator is 4% of the mass of the shell layer monomer.
8. The method for preparing a modified material for PVC according to claim 1, wherein the crosslinking agent is one of 1, 4-butanediol diacrylate, allyl methacrylate or polyethylene glycol dimethacrylate, and the amount of the crosslinking agent is 1% by mass of the core layer monomer.
9. The method of claim 1, wherein the emulsifier is one of sodium dodecylbenzene sulfonate, polyoxyethylene octylphenol ether-10, and sodium hexadecyl sulfonate.
10. The method for preparing a modified material for PVC according to claim 1, wherein the amount of the emulsifier supplemented in the step of preparing the core layer in S3 is 1.5% to 3% of the mass of the core layer monomer.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115466360A (en) * | 2022-11-15 | 2022-12-13 | 山东东临新材料股份有限公司 | Preparation method of SiO2/ACR nano composite material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1418898A (en) * | 2002-11-14 | 2003-05-21 | 河北工业大学 | Process for preparing high shock-resistance polyacrylic ester composite particle grafted vinyl chloride emulsion resin |
| CN104356640A (en) * | 2014-11-11 | 2015-02-18 | 河北工业大学 | Preparation method of polyacrylate compound particles for nylon 6 low-temperature toughening modification |
| CN107082984A (en) * | 2017-05-22 | 2017-08-22 | 新疆中泰化学股份有限公司 | Nano-particle latex and nano particle reinforced tenacity increased vinyl chloride compound resin and preparation method thereof |
-
2022
- 2022-02-26 CN CN202210181775.8A patent/CN114292478A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1418898A (en) * | 2002-11-14 | 2003-05-21 | 河北工业大学 | Process for preparing high shock-resistance polyacrylic ester composite particle grafted vinyl chloride emulsion resin |
| CN104356640A (en) * | 2014-11-11 | 2015-02-18 | 河北工业大学 | Preparation method of polyacrylate compound particles for nylon 6 low-temperature toughening modification |
| CN107082984A (en) * | 2017-05-22 | 2017-08-22 | 新疆中泰化学股份有限公司 | Nano-particle latex and nano particle reinforced tenacity increased vinyl chloride compound resin and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 翟雄伟: "纳米二氧化硅复合核-壳共聚物的制备及其与聚氯乙烯共混改性的应用研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》, no. 5, pages 020 - 54 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115466360A (en) * | 2022-11-15 | 2022-12-13 | 山东东临新材料股份有限公司 | Preparation method of SiO2/ACR nano composite material |
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