CN108250628B - EMO-based high-calcium-carbonate-content hard PVC (polyvinyl chloride) sheet and processing method thereof - Google Patents
EMO-based high-calcium-carbonate-content hard PVC (polyvinyl chloride) sheet and processing method thereof Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
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Abstract
The invention discloses an EMO-based high-calcium carbonate hard PVC sheet and a processing method thereof, wherein the EMO-based high-calcium carbonate hard PVC sheet comprises the following components in parts by weight: PVC resin: 80-100 parts of a binder; EMO: 1-5 parts; thermal stabilizer: 1-3 parts; AIM: 3-8 parts; DOTP: 1-2 parts; calcium carbonate: 30-50 parts; fatty acid ester: 0.1 to 0.6 portion. According to the invention, through the compounding of AIM and EMO, the AIM of toughening the high-content calcium carbonate hard PVC sheet by using a small amount of AIM and EMO is achieved, and the high-content calcium carbonate hard PVC sheet is ensured, so that the high-content calcium carbonate hard PVC sheet has good processability, is easy to form, has a simple process, is low in processing cost and has a good application prospect.
Description
Technical Field
The invention relates to an EMO-based high-calcium carbonate-content hard PVC sheet and a processing method thereof, belonging to the technical field of PVC sheet product processing.
Background
Polyvinyl chloride (PVC) plastic is a polymer of vinyl chloride monomer, one of the commonly used thermoplastics. Pure polyvinyl chloride resin cannot be directly thermoformed due to the properties determined by the molecular structure of the pure polyvinyl chloride resin, and impact modifiers, stabilizers, fillers and the like must be added to improve the performance of the pure polyvinyl chloride resin, so that a polyvinyl chloride formula material is prepared, and then the pure polyvinyl chloride resin is processed into various PVC sheet products.
Among them, calcium carbonate is the most widely used inorganic filler in PVC sheets, and adding calcium carbonate to PVC sheets can improve heat resistance, wear resistance, dimensional stability, rigidity, etc. of products and reduce product cost. However, the inorganic filler has poor compatibility with a high polymer material due to the hydrophilic and oleophobic surface characteristics, and the impact strength of the PVC sheet is reduced, so that the processing difficulty is extremely high when the addition amount of calcium carbonate is more than 30% for a hard PVC sheet. How to solve the above problems is a current urgent need.
Disclosure of Invention
The invention aims to solve the problem that the processing difficulty is very high when the addition amount of calcium carbonate is higher than 30 percent for hard PVC sheets in the prior art. According to the EMO-based high-content calcium carbonate hard PVC sheet and the processing method thereof, the AIM of toughening the high-content calcium carbonate hard PVC sheet by using a small amount of AIM and EMO is achieved through compounding of AIM and EMO, the high-content calcium carbonate hard PVC sheet is ensured, and the high-content calcium carbonate hard PVC sheet has good processability, is easy to form, is simple in process and low in processing cost, and has a good application prospect.
In order to achieve the purpose, the invention adopts the technical scheme that:
an EMO-based high-calcium carbonate hard PVC sheet comprises the following components in parts by weight:
PVC resin: 80-100 parts of a binder;
EMO: 1-5 parts;
thermal stabilizer: 1-3 parts;
AIM: 3-8 parts;
DOTP: 1-2 parts;
calcium carbonate: 30-50 parts;
fatty acid ester: 0.1 to 0.6 portion of,
the EMO is a toughening synergist.
In the EMO-based high-calcium carbonate-content rigid PVC sheet, the heat stabilizer is methyl tin mercaptide.
The EMO-based high-calcium carbonate-content hard PVC sheet comprises the following components in parts by weight:
PVC resin: 100 parts of (A);
EMO: 3 parts of a mixture;
methyl tin mercaptide: 2 parts of (1);
AIM: 3 parts of a mixture;
DOTP: 1 part;
calcium carbonate: 40 parts of a mixture;
fatty acid ester: 0.4 part by weight of a reaction kettle,
the EMO is a toughening synergist.
The EMO-based high-calcium carbonate-content hard PVC sheet comprises the following components in parts by weight:
PVC resin: 100 parts of (A);
EMO: 4 parts of a mixture;
methyl tin mercaptide: 2 parts of (1);
AIM: 5 parts of a mixture;
DOTP: 1 part;
calcium carbonate: 50 parts of a mixture;
fatty acid ester: 0.5 part by weight of a reaction kettle,
the EMO is a toughening synergist.
A processing method of a high-calcium carbonate hard PVC sheet based on EMO comprises the following steps,
step (A), preparing raw materials, weighing and uniformly stirring the raw materials according to the raw material composition of the EMO-based high-content calcium carbonate hard PVC sheet, wherein the raw materials comprise the following components in parts by weight: PVC resin: 80-100 parts of a binder; EMO: 1-5 parts; thermal stabilizer: 1-3 parts; AIM: 3-8 parts; DOTP: 1-2 parts; calcium carbonate: 30-50 parts; fatty acid ester: 0.1-0.6 part;
step (B), hot and cold mixing, namely, hot mixing the uniformly stirred raw materials in a hot mixer at 105-115 ℃, wherein the hot mixing time is 6-8min, and then cold mixing the raw materials in a cold mixer at 40-55 ℃, wherein the hot mixing time is 1.5-2 min;
step (C), curing, namely standing the hot and cold mixed raw materials for 6-7 hours to cure the raw materials;
extruding, namely feeding the cured raw materials into a screw extruder, wherein the rotating speed of the screw is 32-40 r/min, the temperature of a neck ring mold connector is 180-205 ℃, the temperature of a neck ring mold is 185-195 ℃, and extruding high-content calcium carbonate hard PVC sheets;
and (E) cooling, namely cooling the extruded high-content calcium carbonate hard PVC sheet to 20-30 ℃ by using an air cooler.
In the processing method of the EMO-based high-calcium carbonate hard PVC sheet, the heat stabilizer is methyl tin mercaptide.
The processing method of the EMO-based high-calcium carbonate hard PVC sheet comprises the following steps,
step (A1), preparing raw materials, weighing and uniformly stirring the raw materials according to the raw material composition of the smoke suppression PVC sheet based on the hollow glass beads, wherein the raw materials comprise the following components in parts by weight: PVC resin: 100 parts of (A); EMO: 3 parts of a mixture; methyl tin mercaptide: 2 parts of (1); AIM: 3 parts of a mixture; DOTP: 1 part; calcium carbonate: 40 parts of a mixture; fatty acid ester: 0.4 part;
step (B1), hot and cold mixing, namely, hot mixing the uniformly stirred raw materials in a hot mixer at 105 ℃, wherein the hot mixing time is 8min, then sending the raw materials into a cold mixer at 55 ℃, and cold mixing for 2 min;
step (C1), curing, namely, standing the hot and cold mixed raw materials for 7 hours to cure the raw materials;
step (D1), extruding, namely feeding the cured raw materials into a screw extruder, wherein the rotating speed of the screw is 32r/min, the temperature of a neck ring mold connector is 180 ℃, the temperature of a neck ring mold is 195 ℃, and extruding high-content calcium carbonate hard PVC sheets;
and (E1), cooling, namely cooling the extruded high-calcium-carbonate-content hard PVC sheet to 20-30 ℃ by using an air cooler.
The processing method of the EMO-based high-calcium carbonate hard PVC sheet comprises the following steps,
step (A2), preparing raw materials, weighing and uniformly stirring the raw materials according to the raw material composition of the EMO-based high-calcium carbonate hard PVC sheet, wherein the raw materials comprise the following components in parts by weight: PVC resin: 100 parts of (A); EMO: 4 parts of a mixture; methyl tin mercaptide: 2 parts of (1); AIM: 5 parts of a mixture; DOTP: 1 part; calcium carbonate: 50 parts of a mixture; fatty acid ester: 0.5 part;
step (B2), hot and cold mixing, namely, hot mixing the uniformly stirred raw materials in a hot mixer at 115 ℃ for 6min, and then sending the mixture into a cold mixer at 40 ℃ for cold mixing for 2 min;
step (C2), curing, namely, standing the hot and cold mixed raw materials for 6 hours to cure the raw materials;
step (D2), extruding, namely feeding the cured raw materials into a screw extruder, wherein the rotating speed of the screw is 40r/min, the temperature of a neck ring mold connector is 205 ℃, the temperature of the neck ring mold is 185 ℃, and extruding high-content calcium carbonate hard PVC sheets;
and (E2), cooling, namely cooling the extruded high-calcium-carbonate-content hard PVC sheet to 20-30 ℃ by using an air cooler.
The invention has the beneficial effects that: according to the EMO-based high-content calcium carbonate hard PVC sheet and the processing method thereof, the AIM of toughening the high-content calcium carbonate hard PVC sheet by using a small amount of AIM and EMO is achieved through compounding of AIM and EMO, the high-content calcium carbonate hard PVC sheet is ensured, and the high-content calcium carbonate hard PVC sheet has good processability, is easy to form, is simple in process and low in processing cost, and has a good application prospect.
Drawings
FIG. 1 is a flow chart of the method for processing EMO-based high calcium carbonate-content rigid PVC sheets.
Detailed Description
The invention will be further explained with reference to the drawings attached to the specification. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
According to the EMO-based high-calcium carbonate hard PVC sheet and the processing method thereof, through the compounding of AIM (acrylate core-shell polymer) and EMO (ethylene-n-butyl acrylate-carbon monoxide terpolymer), AIM is an impact modifier, EMO is a toughening synergist, and the AIM and the EMO can generate a synergistic effect together, so that the AIM dosage can be reduced and the processability is improved while the toughening is effectively realized, the AIM of toughening the high-calcium carbonate hard PVC sheet by using a small amount of AIM and EMO is achieved, the high-calcium carbonate hard PVC sheet is ensured, the high-calcium carbonate hard PVC sheet has good processability, is easy to form, the process is simple, the processing cost is low, and the EMO-based high-calcium carbonate hard PVC sheet specifically comprises the following components in parts by weight:
PVC resin: 80-100 parts of a binder;
EMO: 1-5 parts;
thermal stabilizer: 1-3 parts;
AIM: 3-8 parts;
DOTP: 1-2 parts;
calcium carbonate: 30-50 parts;
fatty acid ester: 0.1 to 0.6 portion of,
the EMO is a toughening synergist.
Preferably, the heat stabilizer is methyl tin mercaptide, so that the stability of the processing process can be ensured, and the DOTP is a plasticizer, so that the plasticity of the EMO-based high-content calcium carbonate hard PVC sheet in the extrusion process is further improved.
The AIM of toughening the high-content calcium carbonate hard PVC sheet by using less AIM and EMO through compounding AIM (acrylate core-shell polymer) and EMO (ethylene-n-butyl acrylate-carbon monoxide terpolymer) is achieved, and the high-content calcium carbonate hard PVC sheet has good processability, and the principle is as follows,
firstly, EMO is ethylene-n-butyl acrylate-carbon monoxide ternary copolymer, ethylene and n-butyl acrylate are elastic groups, and the toughness of the system is improved by adding the ethylene-n-butyl acrylate-carbon monoxide ternary copolymer and the ethylene-n-butyl acrylate; carbon monoxide group has increased the interface cohesion of PVC sheet and calcium carbonate, n-butyl acrylate has promoted the plastify of PVC sheet, the more fast melting of the granule in making the PVC sheet becomes primary particle, the combined action of two groups has promoted the better faster cladding calcium carbonate particle of PVC sheet, the existence of ethylene group has reduced the fuse-element viscosity, the mobility of system has been promoted, this problem that high filling system mobility and plastify are bad has just been solved, impact strength has been promoted through the improvement of plastification degree, in addition, good mobility has also reduced shear heat, the intensity loss because of being heated has been reduced.
As shown in fig. 1, the method for processing an EMO-based high calcium carbonate-containing rigid PVC sheet according to the present invention comprises the steps of,
step (A), preparing raw materials, weighing and uniformly stirring the raw materials according to the raw material composition of the EMO-based high-content calcium carbonate hard PVC sheet, wherein the raw materials comprise the following components in parts by weight: PVC resin: 80-100 parts of a binder; EMO: 1-5 parts; thermal stabilizer: 1-3 parts; AIM: 3-8 parts; DOTP: 1-2 parts; calcium carbonate: 30-50 parts; fatty acid ester: 0.1-0.6 part;
step (B), hot and cold mixing, namely, hot mixing the uniformly stirred raw materials in a hot mixer at 105-115 ℃, wherein the hot mixing time is 6-8min, and then cold mixing the raw materials in a cold mixer at 40-55 ℃, wherein the hot mixing time is 1.5-2 min;
step (C), curing, namely standing the hot and cold mixed raw materials for 6-7 hours to cure the raw materials;
extruding, namely feeding the cured raw materials into a screw extruder, wherein the rotating speed of the screw is 32-40 r/min, the temperature of a neck ring mold connector is 180-205 ℃, the temperature of a neck ring mold is 185-195 ℃, and extruding high-content calcium carbonate hard PVC sheets;
and (E) cooling, namely cooling the extruded high-content calcium carbonate hard PVC sheet to 20-30 ℃ by using an air cooler.
Preferably, the heat stabilizer is methyl tin mercaptide.
The following description will be made of specific examples according to the EMO-based high calcium carbonate-containing rigid PVC sheet and the method for manufacturing the same of the present invention,
example 1, a smoke suppression PVC sheet based on hollow glass beads was made of raw materials, weighed and stirred uniformly, the raw materials comprising the following components in parts by weight: PVC resin: 100 parts of (A); EMO: 3 parts of a mixture; methyl tin mercaptide: 2 parts of (1); AIM: 3 parts of a mixture; DOTP: 1 part; calcium carbonate: 40 parts of a mixture; fatty acid ester: 0.4 part.
The production process of example 1 is as follows:
step (A1), preparing raw materials, weighing and uniformly stirring the raw materials according to the raw material composition of the smoke suppression PVC sheet based on the hollow glass beads, wherein the raw materials comprise the following components in parts by weight: PVC resin: 100 parts of (A); EMO: 3 parts of a mixture; methyl tin mercaptide: 2 parts of (1); AIM: 3 parts of a mixture; DOTP: 1 part; calcium carbonate: 40 parts of a mixture; fatty acid ester: 0.4 part;
step (B1), hot and cold mixing, namely, hot mixing the uniformly stirred raw materials in a hot mixer at 105 ℃, wherein the hot mixing time is 8min, then sending the raw materials into a cold mixer at 55 ℃, and cold mixing for 2 min;
step (C1), curing, namely, standing the hot and cold mixed raw materials for 7 hours to cure the raw materials;
step (D1), extruding, namely feeding the cured raw materials into a screw extruder, wherein the rotating speed of the screw is 32r/min, the temperature of a neck ring mold connector is 180 ℃, the temperature of a neck ring mold is 195 ℃, and extruding high-content calcium carbonate hard PVC sheets;
and (E1), cooling, namely cooling the extruded high-calcium-carbonate-content hard PVC sheet to 20-30 ℃ by using an air cooler.
Example 2, the raw material composition of the hard PVC sheet with high calcium carbonate content based on EMO was weighed and stirred uniformly, and the raw material included the following components in parts by weight: PVC resin: 100 parts of (A); EMO: 4 parts of a mixture; methyl tin mercaptide: 2 parts of (1); AIM: 5 parts of a mixture; DOTP: 1 part; calcium carbonate: 50 parts of a mixture; fatty acid ester: 0.5 part.
The production process of example 2 is as follows:
step (A2), preparing raw materials, weighing and uniformly stirring the raw materials according to the raw material composition of the EMO-based high-calcium carbonate hard PVC sheet, wherein the raw materials comprise the following components in parts by weight: PVC resin: 100 parts of (A); EMO: 4 parts of a mixture; methyl tin mercaptide: 2 parts of (1); AIM: 5 parts of a mixture; DOTP: 1 part; calcium carbonate: 50 parts of a mixture; fatty acid ester: 0.5 part;
step (B2), hot and cold mixing, namely, hot mixing the uniformly stirred raw materials in a hot mixer at 115 ℃ for 6min, and then sending the mixture into a cold mixer at 40 ℃ for cold mixing for 1.5 min;
step (C2), curing, namely, standing the hot and cold mixed raw materials for 6 hours to cure the raw materials;
step (D2), extruding, namely feeding the cured raw materials into a screw extruder, wherein the rotating speed of the screw is 40r/min, the temperature of a neck ring mold connector is 205 ℃, the temperature of the neck ring mold is 185 ℃, and extruding high-content calcium carbonate hard PVC sheets;
and (E2), cooling, namely cooling the extruded high-calcium-carbonate-content hard PVC sheet to 20-30 ℃ by using an air cooler.
Experiments show that the two examples and the traditional high-calcium carbonate hard PVC sheet have the specific effects shown in the following table,
as can be seen from the above table, the tensile yield stress, notched impact strength and Vicat of the two examples are greatly improved compared with the performance of the conventional high calcium carbonate content rigid PVC sheet.
In conclusion, the EMO-based high-content calcium carbonate hard PVC sheet and the processing method thereof achieve the purpose of toughening the high-content calcium carbonate hard PVC sheet by using a small amount of AIM and EMO through the compounding of AIM and EMO, ensure the high-content calcium carbonate hard PVC sheet, have good processability, are easy to form, have simple process and low processing cost, and have good application prospect.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (8)
1. The EMO-based high-calcium carbonate hard PVC sheet is characterized by comprising the following components in parts by weight:
PVC resin: 80-100 parts of a binder;
ethylene-n-butyl acrylate-carbon monoxide terpolymer: 1-5 parts;
thermal stabilizer: 1-3 parts;
acrylate core-shell polymer: 3-8 parts;
DOTP: 1-2 parts;
calcium carbonate: 30-50 parts;
fatty acid ester: 0.1 to 0.6 portion of,
the ethylene-n-butyl acrylate-carbon monoxide ternary copolymer is a toughening synergist.
2. The EMO-based, high calcium carbonate rigid PVC sheet according to claim 1, wherein the thermal stabilizer is methyl tin mercaptide.
3. The EMO-based high-calcium carbonate rigid PVC sheet according to claim 2, which comprises the following components in parts by weight:
PVC resin: 100 parts of (A);
ethylene-n-butyl acrylate-carbon monoxide terpolymer: 3 parts of a mixture;
methyl tin mercaptide: 2 parts of (1);
acrylate core-shell polymer: 3 parts of a mixture;
DOTP: 1 part;
calcium carbonate: 40 parts of a mixture;
fatty acid ester: 0.4 part by weight of a reaction kettle,
the ethylene-n-butyl acrylate-carbon monoxide ternary copolymer is a toughening synergist.
4. The EMO-based high-calcium carbonate rigid PVC sheet according to claim 2, which comprises the following components in parts by weight:
PVC resin: 100 parts of (A);
ethylene-n-butyl acrylate-carbon monoxide terpolymer: 4 parts of a mixture;
methyl tin mercaptide: 2 parts of (1);
acrylate core-shell polymer: 5 parts of a mixture;
DOTP: 1 part;
calcium carbonate: 50 parts of a mixture;
fatty acid ester: 0.5 part by weight of a reaction kettle,
the ethylene-n-butyl acrylate-carbon monoxide ternary copolymer is a toughening synergist.
5. The processing method of the EMO-based high-calcium carbonate hard PVC sheet is characterized by comprising the following steps,
step (A), preparing raw materials, namely, EMO-based high-calcium carbonate hard PVC sheets, weighing and uniformly stirring the raw materials, wherein the raw materials comprise the following components in parts by weight: PVC resin: 80-100 parts of a binder; ethylene-n-butyl acrylate-carbon monoxide terpolymer: 1-5 parts; thermal stabilizer: 1-3 parts; acrylate core-shell polymer: 3-8 parts; DOTP: 1-2 parts; calcium carbonate: 30-50 parts; fatty acid ester: 0.1-0.6 part;
step (B), hot and cold mixing, namely hot mixing the uniformly stirred raw materials in a hot mixer at 105-115 ℃, wherein the hot mixing time is 6-8min, and then cold mixing in a cold mixer at 40-55 ℃, wherein the cold mixing time is 1.5-2 min;
step (C), curing, namely standing the hot and cold mixed raw materials for 6-7 hours to cure the raw materials;
extruding, namely feeding the cured raw materials into a screw extruder, wherein the rotating speed of the screw is 32-40 r/min, the temperature of a neck ring mold connector is 180-205 ℃, the temperature of a neck ring mold is 185-195 ℃, and extruding high-content calcium carbonate hard PVC sheets;
and (E) cooling, namely cooling the extruded high-content calcium carbonate hard PVC sheet to 20-30 ℃ by using an air cooler.
6. The method for processing an EMO-based high calcium carbonate rigid PVC sheet according to claim 5, wherein the heat stabilizer is methyl tin mercaptide.
7. The method for processing EMO-based high calcium carbonate rigid PVC sheets according to claim 6, comprising the steps of,
step (A1), preparing raw materials, weighing and uniformly stirring the raw materials based on the raw materials of the EMO high-content calcium carbonate hard PVC sheet, wherein the raw materials comprise the following components in parts by weight: PVC resin: 100 parts of (A); ethylene-n-butyl acrylate-carbon monoxide terpolymer: 3 parts of a mixture; methyl tin mercaptide: 2 parts of (1); acrylate core-shell polymer: 3 parts of a mixture; DOTP: 1 part; calcium carbonate: 40 parts of a mixture; fatty acid ester: 0.4 part;
step (B1), hot and cold mixing, namely, hot mixing the uniformly stirred raw materials in a hot mixer at 105 ℃, wherein the hot mixing time is 8min, then sending the raw materials into a cold mixer at 55 ℃, and cold mixing for 2 min;
step (C1), curing, namely, standing the hot and cold mixed raw materials for 7 hours to cure the raw materials;
step (D1), extruding, namely feeding the cured raw materials into a screw extruder, wherein the rotating speed of the screw is 32r/min, the temperature of a neck ring mold connector is 180 ℃, the temperature of a neck ring mold is 195 ℃, and extruding high-content calcium carbonate hard PVC sheets;
and (E1), cooling, namely cooling the extruded high-calcium-carbonate-content hard PVC sheet to 20-30 ℃ by using an air cooler.
8. The method for processing EMO-based high calcium carbonate rigid PVC sheets according to claim 6, comprising the steps of,
step (A2), preparing raw materials, weighing and uniformly stirring the raw materials according to the raw material composition of the EMO-based high-calcium carbonate hard PVC sheet, wherein the raw materials comprise the following components in parts by weight: PVC resin: 100 parts of (A); ethylene-n-butyl acrylate-carbon monoxide terpolymer: 4 parts of a mixture; methyl tin mercaptide: 2 parts of (1); acrylate core-shell polymer: 5 parts of a mixture; DOTP: 1 part; calcium carbonate: 50 parts of a mixture; fatty acid ester: 0.5 part;
step (B2), hot and cold mixing, namely, hot mixing the uniformly stirred raw materials in a hot mixer at 115 ℃ for 6min, and then sending the mixture into a cold mixer at 40 ℃ for cold mixing for 1.5 min;
step (C2), curing, namely, standing the hot and cold mixed raw materials for 6 hours to cure the raw materials;
step (D2), extruding, namely feeding the cured raw materials into a screw extruder, wherein the rotating speed of the screw is 40r/min, the temperature of a neck ring mold connector is 205 ℃, the temperature of the neck ring mold is 185 ℃, and extruding high-content calcium carbonate hard PVC sheets;
and (E2), cooling, namely cooling the extruded high-calcium-carbonate-content hard PVC sheet to 20-30 ℃ by using an air cooler.
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| AIM增韧剂的合成及其增韧PVC的研究;吴广峰等;《塑料科技》;20080229;第36卷(第2期);第94-97页 * |
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| CN108250628A (en) | 2018-07-06 |
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