CN117551324B - High-temperature-resistant low-temperature-resistant antibacterial PVC material and preparation method thereof - Google Patents
High-temperature-resistant low-temperature-resistant antibacterial PVC material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 84
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 59
- 239000011347 resin Substances 0.000 claims abstract description 36
- 229920005989 resin Polymers 0.000 claims abstract description 36
- 239000006084 composite stabilizer Substances 0.000 claims abstract description 31
- 239000000314 lubricant Substances 0.000 claims abstract description 21
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 12
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 22
- -1 quaternary ammonium salt compound Chemical class 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- VMZVBRIIHDRYGK-UHFFFAOYSA-N 2,6-ditert-butyl-4-[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VMZVBRIIHDRYGK-UHFFFAOYSA-N 0.000 claims description 13
- 239000003381 stabilizer Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- CHUGKEQJSLOLHL-UHFFFAOYSA-N 2,2-Bis(bromomethyl)propane-1,3-diol Chemical compound OCC(CO)(CBr)CBr CHUGKEQJSLOLHL-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000005662 Paraffin oil Substances 0.000 claims description 5
- 230000000845 anti-microbial effect Effects 0.000 claims description 5
- 239000011276 wood tar Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 239000004088 foaming agent Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 238000005187 foaming Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000012188 paraffin wax Substances 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 3
- 239000001993 wax Substances 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims 1
- 238000001556 precipitation Methods 0.000 abstract description 12
- 230000003647 oxidation Effects 0.000 abstract description 10
- 238000007254 oxidation reaction Methods 0.000 abstract description 10
- 239000004800 polyvinyl chloride Substances 0.000 description 106
- 229920000915 polyvinyl chloride Polymers 0.000 description 105
- 230000000052 comparative effect Effects 0.000 description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 230000001105 regulatory effect Effects 0.000 description 7
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- YNGDWRXWKFWCJY-UHFFFAOYSA-N 1,4-Dihydropyridine Chemical compound C1C=CNC=C1 YNGDWRXWKFWCJY-UHFFFAOYSA-N 0.000 description 2
- QCNUSBDGDRMPKD-UHFFFAOYSA-N 4-bromobutane-1,3-diol Chemical compound OCCC(O)CBr QCNUSBDGDRMPKD-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- DWPDSISGRAWLLV-JHZYRPMRSA-L calcium;(1r,4ar,4br,10ar)-1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylate Chemical compound [Ca+2].C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C([O-])=O.C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C([O-])=O DWPDSISGRAWLLV-JHZYRPMRSA-L 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- WGIWBXUNRXCYRA-UHFFFAOYSA-H trizinc;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WGIWBXUNRXCYRA-UHFFFAOYSA-H 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011746 zinc citrate Substances 0.000 description 2
- 229940068475 zinc citrate Drugs 0.000 description 2
- 235000006076 zinc citrate Nutrition 0.000 description 2
- RXVMKCWWKQUKDI-UHFFFAOYSA-N (sulfonylamino)urea;toluene Chemical compound CC1=CC=CC=C1.NC(=O)NN=S(=O)=O RXVMKCWWKQUKDI-UHFFFAOYSA-N 0.000 description 1
- FUIQBJHUESBZNU-UHFFFAOYSA-N 2-[(dimethylazaniumyl)methyl]phenolate Chemical group CN(C)CC1=CC=CC=C1O FUIQBJHUESBZNU-UHFFFAOYSA-N 0.000 description 1
- NFVPEIKDMMISQO-UHFFFAOYSA-N 4-[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC=C(O)C=C1 NFVPEIKDMMISQO-UHFFFAOYSA-N 0.000 description 1
- 208000035143 Bacterial infection Diseases 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 208000022362 bacterial infectious disease Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08L27/02—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 not modified by chemical after-treatment
- C08L27/04—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 not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention relates to the technical field of PVC, in particular to a high-temperature-resistant low-temperature-resistant antibacterial PVC material and a preparation method thereof, wherein the prepared high-temperature-resistant low-temperature-resistant antibacterial PVC material comprises the following components in parts by mass: 80-100 parts of PVC resin, 1-5 parts of composite stabilizer, 0.5-0.9 part of lubricant and 5-20 parts of auxiliary agent; the polymerization degree of the PVC resin is 1000-1800; the auxiliary agent has the structure that:wherein R is 1 Is C18-C28 fatty alkane. The high-temperature-resistant low-temperature-resistant antibacterial PVC material disclosed by the invention is high in high temperature resistance, good in low temperature resistance, good in antibacterial property and oxidation resistance, and capable of being widely applied to various fields, especially in the medical field and furniture; the high-temperature-resistant low-temperature-resistant antibacterial PVC material disclosed by the invention has the advantages of good intersolubility of each component and no precipitation phenomenon.
Description
Technical Field
The invention relates to the technical field of PVC, in particular to a high-temperature-resistant low-temperature-resistant antibacterial PVC material and a preparation method thereof.
Background
Polyvinyl chloride (PVC), a plastic material widely used in a variety of fields. It has the characteristics of low price, flame retardance, no toxicity, good electrical insulation property, good processability and the like, is widely applied to the fields of aerospace, medical treatment, automobiles, buildings and the like. However, since PVC has poor heat resistance and is highly Wen Yifa decomposed, it is necessary to add some heat stabilizer to the PVC material to reduce the decomposition of PVC, and in order to improve the mechanical properties, some auxiliary agents such as toughening agent and lubricant are added to the PVC material to enhance the properties.
PVC is widely applied in the medical field, such as blood bags, catheters and the like, and because the working environment is in a place where bacteria gather for a long time, bacteria can be attached to the surface of the PVC, so that a patient is easy to cause bacterial infection when using medical equipment prepared from the PVC material, and the demand for PVC antibacterial materials is continuously increasing.
At present, researchers are carrying out a great deal of research on the high temperature resistance of PVC materials, but the PVC materials have poor mechanical properties in low temperature environment, and the phenomena of brittle fracture and the like occur to influence the use of the PVC materials, so that the low temperature resistance of the PVC materials becomes an important research direction.
For example, the PVC modified material disclosed in CN101979434B, a low temperature resistant medical PVC modified material, has good low temperature resistance and excellent precipitation resistance, but the PVC modified material disclosed in the publication is mostly used in the medical field, and the antibacterial capability of the material is not mentioned and solved.
The PVC material disclosed in CN109627626B PVC foaming antibacterial board and the preparation method thereof has better antibacterial property and mechanical property, but the PVC material does not mention and solve the low-temperature property of the material, and the application range is limited.
And as disclosed in CN111040411B, a plastic material with low temperature resistance and antibacterial property has low temperature resistance, oxidation resistance and antibacterial property, but the plastic material is not disclosed to be applicable to PVC materials, and the stabilizing effect is not obvious when the adopted stearate is singly used, and auxiliary stabilizers are mostly needed to be compounded for use.
Therefore, it is urgent to develop a PVC material which is resistant to both low and high temperatures and has antibacterial properties.
Disclosure of Invention
The invention mainly aims to provide a high-temperature-resistant low-temperature-resistant antibacterial PVC material and a preparation method thereof.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the invention provides a high-temperature-resistant low-temperature-resistant antibacterial PVC material, which comprises the following components in parts by mass: 80-100 parts of PVC resin, 1-5 parts of composite stabilizer, 0.5-0.9 part of lubricant and 5-20 parts of auxiliary agent;
the polymerization degree of the PVC resin is 1000-1800;
the auxiliary agent has the structure that:
wherein R is 1 Is C18-C28 fatty alkane.
The auxiliary agent structure contains the quaternary ammonium salt structure, the antibacterial effect can be well achieved, the quaternary ammonium salt has hydrophilicity, the phenomenon that the quaternary ammonium salt cannot be completely and stably existing in the PVC material and is easy to precipitate is easy to occur, the applicant is connected with long-chain fatty alkane at the upper end and the lower end through modifying the hydroxyl structure of the quaternary ammonium salt structure, the oleophilic performance and the low-temperature resistance of the auxiliary agent are improved, the stability of the auxiliary agent in PVC resin is better, and in addition, the auxiliary agent structure is provided with hindered phenol groups, so that the oxidation resistance of the PVC material is improved. In addition, the applicant can make the intersolubility among the components in the system better by regulating and controlling the polymerization degree of the PVC resin, and enhance the precipitation resistance of the PVC material.
In some embodiments, the lubricant is one or more of polyethylene wax, paraffin oil, and chlorinated paraffin.
Preferably, the lubricant is paraffin oil.
In some embodiments, the mass portion ratio of the PVC resin to the auxiliary agent is 1 (0.07-0.17).
Preferably, the mass part ratio of the PVC resin to the auxiliary agent is 1 (0.12).
As the auxiliary agent has the quaternary ammonium salt structure, the applicant can better prevent the phenomenon of precipitation and migration during use by regulating the proportion of the PVC resin and the auxiliary agent, so that the PVC material is more stable.
In some embodiments, the adjuvant comprises the following component raw materials: 2, 6-di-tert-butyl-p- (dimethylaminomethyl) phenol, 2-bis (bromomethyl) -1, 3-propanediol and C18-C28 fatty acids.
Preferably, the auxiliary agent comprises the following raw materials: 2, 6-di-tert-butyl-p- (dimethylaminomethyl) phenol, 2-bis (bromomethyl) -1, 3-propanediol and wooden coke acid.
In some embodiments, the method of preparing the adjuvant comprises the steps of:
(a) Adding 2, 6-di-tert-butyl p- (dimethylaminomethyl) phenol into a solvent, uniformly stirring, adding 2, 2-bis (bromomethyl) -1, 3-propanediol, heating to a reflux state, and stirring for 24-28 h to obtain a quaternary ammonium salt compound;
(b) Mixing the quaternary ammonium salt compound in the step (a) with fatty acid of C18-C28, adding an acid regulator to adjust the pH value to 1-6, heating to 60-80 ℃, and stirring for 4-6 h to obtain the auxiliary agent.
Preferably, the preparation method of the auxiliary agent comprises the following steps:
(a) Adding 2, 6-di-tert-butyl p- (dimethylaminomethyl) phenol into isopropanol, uniformly stirring, adding 2, 2-bis (bromomethyl) -1, 3-propanediol, heating to 85 ℃, and stirring for 26 hours to obtain a quaternary ammonium salt compound;
(b) Mixing the quaternary ammonium salt compound in the step (a) with wood tar acid, adding 2N sulfuric acid to adjust the pH to 3, heating to 70 ℃, and stirring for 5 hours to obtain the auxiliary agent.
In some embodiments, the molar ratio of 2, 6-di-tert-butyl-p- (dimethylaminomethyl) phenol to 2, 2-bis (bromomethyl) -1, 3-propanediol in step (a) is 1 (0.3-0.5).
Preferably, in the step (a), the molar ratio of the 2, 6-di-tert-butyl-p- (dimethylaminomethyl) phenol to the 2, 2-bis (bromomethyl) -1, 3-propanediol is 1:0.4.
The 2, 2-bis (bromomethyl) -1, 3-propanediol contains two hydroxyl groups, the 2, 6-di-tert-butyl p (dimethylaminomethyl) phenol contains one amino group, and the two hydroxyl groups in the 2, 2-bis (bromomethyl) -1, 3-propanediol and the amino groups of the 2, 6-di-tert-butyl p (dimethylaminomethyl) phenol form a quaternary ammonium salt structure completely through regulating the molar ratio of the two amino groups.
In some embodiments, in step (a), the solvent is one or more of isopropanol, methanol and tetrahydrofuran and is added in an amount of 10 to 14 volumes of 2, 6-di-tert-butyl-p- (dimethylaminomethyl) phenol mass.
Preferably, in the step (a), the solvent is isopropyl alcohol, and the addition amount is 12 times by volume of the mass of the 2, 6-di-tert-butyl-p- (dimethylaminomethyl) phenol.
In some embodiments, in step (b), the molar ratio of quaternary ammonium compound to fatty acid of C18-C28 is 1 (2.2-2.4).
Preferably, in the step (b), the molar ratio of the quaternary ammonium salt compound to the fatty acid of C18-C28 is 1:2.3.
The quaternary ammonium salt compound contains two alcohol hydroxyl structures, has stronger hydrophilic performance, and can enhance the oleophylic capacity of the auxiliary agent by modifying hydroxyl groups, so that the auxiliary agent is more stable in the PVC material and precipitation phenomenon is prevented; the molar ratio of the quaternary ammonium salt compound to the fatty acid of C18-C28 is regulated to ensure that the quaternary ammonium salt compound reacts more completely, so that the yield of the auxiliary agent is improved.
In some embodiments, the method of preparing a composite stabilizer comprises the steps of:
s1, mixing and stirring 1-5 parts of auxiliary stabilizer, 1-5 parts of ultraviolet absorbent, 1-15 parts of modified silicon dioxide, 3-9 parts of foaming agent, 20-25 parts of foaming stabilizer and 1-7 parts of filler for 10-20 min;
s2, adding 20-50 parts of main stabilizer into the mixture obtained in the step S1, heating to 40-60 ℃, stirring for 30-60 min, and cooling to room temperature to obtain the composite stabilizer.
Preferably, the preparation method of the composite stabilizer comprises the following steps:
s1, mixing and stirring 2.8 parts of auxiliary stabilizer, 3 parts of ultraviolet absorber, 7 parts of modified silicon dioxide, 3.4 parts of tosyl semicarbazide, 2.6 parts of microsphere swelling agent, 23 parts of methyl silicone oil and 4 parts of talcum powder for 15min;
s2, adding 35 parts of a main stabilizer of calcium abietate and zinc citrate in a molar ratio of 1:1 into the mixture in the step S1, heating to 50 ℃, stirring for 45min, and cooling to 28 ℃ to obtain the composite stabilizer.
In some embodiments, the modified silica is octaepoxycyclohexylethyl POSS modified silica.
In some embodiments, the method of making the octaepoxycyclohexylethyl POSS modified silica comprises the steps of: 100g of silicon dioxide and 130mL of water are fully and uniformly mixed, the pH is regulated to 10 by using a 2N sodium carbonate aqueous solution, the temperature is raised to 110 ℃, 3g of octaepoxycyclohexylethyl POSS is slowly added after stirring for a period of time, and the octaepoxycyclohexylethyl POSS is obtained after stirring for 2 hours.
The invention also provides a preparation method of the high-temperature-resistant low-temperature-resistant antibacterial PVC material, which comprises the following steps: the PVC resin, the composite stabilizer, the lubricant and the auxiliary agent are weighed according to the mass parts, uniformly mixed at 140-160 ℃, extruded and granulated by a double screw extruder to obtain the high-temperature-resistant low-temperature-resistant antibacterial PVC material.
Compared with the prior art, the invention has the following beneficial effects:
(1) On one hand, the antibacterial PVC material can still keep toughness at low temperature, has no brittle fracture phenomenon, and has excellent oxidation resistance; on the other hand, the degradation capability of PVC is reduced in a high-temperature environment; in addition, the antibacterial capability is provided, so that the antibacterial agent is more suitable for the fields of medical appliances and furniture; in addition, the compatibility of each component and the PVC resin can be further improved by regulating and controlling the polymerization degree of the PVC resin.
(2) The invention synthesizes a multifunctional auxiliary agent, which can lead the PVC resin to have excellent oxidation resistance, antibiosis and low temperature resistance; in addition, through modifying the hydroxyl in the 2, 2-bis (bromomethyl) -1, 3-propanediol, the auxiliary agent structure has a long-chain fatty structure, the oleophilic performance of the auxiliary agent is enhanced, the auxiliary agent is better mutually dissolved in the PVC material, and the precipitation phenomenon is reduced.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The raw materials used in each of the examples and comparative examples were as follows:
PVC resin is purchased from Bohai chlor alkali new material science and technology Co.Ltd in Hebei; the lubricant is paraffin oil, and is purchased from Shandong Taichang petrochemical technology Co.
Preparation example 1
The composite stabilizer comprises the following components in parts by mass: 35 parts of main stabilizer, 2.8 parts of dihydropyridine, 3 parts of UV-234 type ultraviolet absorber, 7 parts of modified silicon dioxide, 6 parts of foaming agent, 23 parts of methyl silicone oil and 4 parts of talcum powder; the main stabilizer is formed by mixing 1mol of calcium abietate with 1mol of zinc citrate; the blowing agent was mixed from 3.4 parts toluene sulfonylsemicarbazide and 2.6 parts XR-2366 microsphere expansion agent.
The preparation method of the composite stabilizer comprises the following steps:
s1, mixing and stirring dihydropyridine, a UV-234 ultraviolet absorbent, modified silicon dioxide, a foaming agent, methyl silicone oil and talcum powder for 15min to obtain a mixture;
s2, adding the main stabilizer into the mixture obtained in the step S1, heating to 50 ℃, stirring for 45min, and cooling to 28 ℃ to obtain the composite stabilizer.
The preparation method of the modified silicon dioxide is eight-epoxy cyclohexyl ethyl POSS modified silicon dioxide and comprises the following steps: 100g of silicon dioxide and 130mL of water are fully and uniformly mixed, the pH is regulated to 10 by using 2mol/L sodium carbonate aqueous solution, after the temperature is raised to 110 ℃, stirring is carried out for 25min, 3g of octaepoxycyclohexylethyl POSS is slowly added, and after stirring is carried out for 2h, octaepoxycyclohexylethyl POSS modified silicon dioxide is obtained.
Preparation example 2
The preparation method of the auxiliary agent comprises the following steps:
(a) 100g (380 mmol) of 2, 6-di-tert-butyl-p- (dimethylaminomethyl) phenol is added into 1200mL of isopropanol, and the mixture is stirred uniformly, 39.8g (152 mmol) of 2, 2-bis (bromomethyl) -1, 3-propanediol is added, the temperature is raised to 85 ℃, and the mixture is stirred for 26 hours, so as to obtain a quaternary ammonium salt compound;
(b) Mixing 200g (254 mmol) of quaternary ammonium salt compound in the step (a) with 215g (583 mmol) of wood tar acid, adding 2N sulfuric acid to adjust pH to 3, heating to 70 ℃, and stirring for 5h to obtain the auxiliary agent.
Preparation example 3
The preparation method of the auxiliary agent is the same as in preparation example 2, except that the addition amount of the wood tar acid is 112.2g (304 mmol).
Preparation example 4
The preparation method of the auxiliary agent is the same as in preparation example 2, except that equal moles of heptanoic acid are used instead of the wood tar acid.
Preparation example 5
The preparation method of the auxiliary agent is the same as in preparation example 2, except that the 2, 6-di-tert-butyl p- (dimethylaminomethyl) phenol is replaced by equal moles of n-tripropylamine.
Example 1
The high-temperature-resistant low-temperature-resistant antibacterial PVC material comprises the following components in parts by mass: 90 parts of PVC resin, 3 parts of composite stabilizer, 0.7 part of lubricant and 10.8 parts of auxiliary agent. The degree of polymerization of the PVC resin was 1600.
Wherein, the composite stabilizer is prepared by a preparation example 1; the auxiliary agent was prepared in preparation example 2.
The preparation method of the high-temperature-resistant low-temperature-resistant antibacterial PVC material comprises the following steps: the PVC resin, the composite stabilizer, the lubricant and the auxiliary agent are weighed according to the mass parts, uniformly mixed at 150 ℃, extruded and granulated by a double-screw extruder to obtain the high-temperature-resistant low-temperature-resistant antibacterial PVC material.
Example 2
The high-temperature-resistant low-temperature-resistant antibacterial PVC material comprises the following components in parts by mass: 80 parts of PVC resin, 1 part of composite stabilizer, 0.5 part of lubricant and 9.6 parts of auxiliary agent. The polymerization degree of the PVC resin was 1800.
Wherein, the composite stabilizer is prepared by a preparation example 1; the auxiliary agent was prepared in preparation example 2.
The preparation method of the high-temperature-resistant low-temperature-resistant antibacterial PVC material comprises the following steps: the PVC resin, the composite stabilizer, the lubricant and the auxiliary agent are weighed according to the mass parts, uniformly mixed at 140 ℃, extruded and granulated by a double-screw extruder to obtain the high-temperature-resistant low-temperature-resistant antibacterial PVC material.
Example 3
The high-temperature-resistant low-temperature-resistant antibacterial PVC material comprises the following components in parts by mass: 100 parts of PVC resin, 5 parts of composite stabilizer, 0.9 part of lubricant and 12 parts of auxiliary agent. The degree of polymerization of the PVC resin was 1000.
Wherein, the composite stabilizer is prepared by a preparation example 1; the auxiliary agent was prepared in preparation example 2.
The preparation method of the high-temperature-resistant low-temperature-resistant antibacterial PVC material comprises the following steps: the PVC resin, the composite stabilizer, the lubricant and the auxiliary agent are weighed according to the mass parts, uniformly mixed at 160 ℃, extruded and granulated by a double-screw extruder to obtain the high-temperature-resistant low-temperature-resistant antibacterial PVC material.
Example 4
The high-temperature-resistant low-temperature-resistant antibacterial PVC material comprises the following components in parts by mass: 90 parts of PVC resin, 3 parts of composite stabilizer, 0.7 part of lubricant and 6.3 parts of auxiliary agent. The degree of polymerization of the PVC resin was 1300.
Wherein, the composite stabilizer is prepared by a preparation example 1; the auxiliary agent was prepared in preparation example 2.
The preparation method of the high-temperature-resistant low-temperature-resistant antibacterial PVC material comprises the following steps: the PVC resin, the composite stabilizer, the lubricant and the auxiliary agent are weighed according to the mass parts, uniformly mixed at 150 ℃, extruded and granulated by a double-screw extruder to obtain the high-temperature-resistant low-temperature-resistant antibacterial PVC material.
Example 5
The high-temperature-resistant low-temperature-resistant antibacterial PVC material comprises the following components in parts by mass: 90 parts of PVC resin, 3 parts of composite stabilizer, 0.7 part of lubricant and 15.3 parts of auxiliary agent. The degree of polymerization of the PVC resin was 1600.
Wherein, the composite stabilizer is prepared by a preparation example 1; the auxiliary agent was prepared in preparation example 2.
The preparation method of the high-temperature-resistant low-temperature-resistant antibacterial PVC material comprises the following steps: the PVC resin, the composite stabilizer, the lubricant and the auxiliary agent are weighed according to the mass parts, uniformly mixed at 150 ℃, extruded and granulated by a double-screw extruder to obtain the high-temperature-resistant low-temperature-resistant antibacterial PVC material.
Example 6
The embodiment provides a high-temperature-resistant low-temperature-resistant antibacterial PVC material, and the specific embodiment is the same as the embodiment 1, wherein the mass part of the auxiliary agent is 5 parts.
Example 7
This example provides a high temperature and low temperature resistant antimicrobial PVC material, and the specific embodiment is the same as example 1, except that the auxiliary agent is prepared from preparation example 3.
Example 8
This example provides a high temperature and low temperature resistant antimicrobial PVC material, and the specific embodiment is the same as example 1, except that the auxiliary agent is prepared from preparation example 4.
Example 9
This example provides a high temperature and low temperature resistant antimicrobial PVC material, and the specific embodiment is the same as example 1, except that the auxiliary agent is prepared from preparation example 5.
Comparative example 1
This comparative example provides a PVC material, the specific embodiment being the same as example 1, except that no auxiliary agent is added.
Comparative example 2
This comparative example provides a PVC material, the specific embodiment being the same as example 1, except that no composite stabilizer was added.
Comparative example 3
The comparative example provides a high temperature resistant and low temperature resistant antibacterial PVC material, and the specific embodiment is the same as example 1, except that PVC resin is purchased from Ningbo British Co., ltd, and the polymerization degree is 800.
Performance test:
(1) Antibacterial test: the PVC materials of each example and comparative example are subjected to antibacterial test and are detected according to the standard of GB/T21510-2008 nano inorganic material antibacterial property detection method;
(2) Low temperature resistance test: the PVC materials of each example and comparative example are respectively subjected to impact resistance tests at 28 ℃ and-30 ℃ and are tested according to GB/T1843-2008 'determination of impact strength of cantilever beam';
(3) Antioxidation test: the PVC materials of each example and comparative example were placed in a forced air drying oven, the temperature was adjusted to 180 ℃, and heated for 2 hours, and the time for the PVC material to turn yellow and black was observed and recorded.
(4) Anti-precipitation test: after the PVC materials of each example and comparative example were left at 35 ℃ for 500 hours, the appearance was regarded as precipitation by observing whether bubbling, fogging or roughening occurred on the surface of each PVC material.
(5) Heat resistance test: after the PVC materials of each example and comparative example are placed in an environment of 200 ℃ for 120min, the retention rate of tensile strength is tested according to the standard of GB/T1040-1992 plastic tensile property test method;
the test results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the high temperature resistant and low temperature resistant antibacterial PVC materials prepared in examples 1 to 5 have better antibacterial performance, low temperature resistant performance, oxidation resistance and precipitation resistance; in the embodiment 6, the proportion of the PVC resin to the auxiliary agent is changed, so that the content of the auxiliary agent is reduced, and the antibacterial property, the low-temperature resistance and the oxidation resistance of the PVC material are weakened; example 7 the reduction of long chain structure in PVC material resulted in a decrease in impact resistance and low temperature resistance of PVC material due to the change of molar ratio of the pyroligneous acid and the quaternary ammonium salt compound; example 8 because heptanoic acid with equal molar mass is used for replacing the pyroligneous acid, the long-chain low-temperature resistant structure in the PVC material is reduced, and the low-temperature resistant performance of the PVC material is reduced; example 9 the oxidation resistance of the system was reduced by using equimolar mass of n-tripropylamine instead of 2, 6-di-t-butyl p- (dimethylaminomethyl) phenol, resulting in blackening and yellowing of the PVC material; in the comparative example 1, no auxiliary agent is added, so that the antibacterial property of the PVC material is reduced, and the normal-temperature impact strength, the low-temperature impact strength and the oxidation resistance are all reduced; comparative example 2, since no composite stabilizer was added, the PVC material was degraded at high temperature, resulting in a decrease in tensile strength retention after high temperature; comparative example 3 shows that the mutual solubility between the components in the system is deteriorated due to the change of the polymerization degree of the PVC resin, and a migration and precipitation phenomenon occurs, and in addition, the impact resistance and low temperature resistance of the PVC material are also reduced due to the easy precipitation. The detection result shows that the high-temperature-resistant low-temperature-resistant antibacterial PVC material prepared by the invention has better antibacterial performance, high-temperature-resistant low-temperature-resistant performance, oxidation resistance and precipitation resistance.
Finally, it should be noted that the above-mentioned embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same, and although the present invention has been described in detail with reference to examples, it should be understood by those skilled in the art that modifications and equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention, and all such modifications and equivalents are intended to be encompassed in the scope of the claims of the present invention.
Claims (4)
1. The high-temperature-resistant low-temperature-resistant antibacterial PVC material is characterized by being prepared from the following components in parts by mass: 80-100 parts of PVC resin, 1-5 parts of composite stabilizer, 0.5-0.9 part of lubricant and 5-20 parts of auxiliary agent;
the polymerization degree of the PVC resin is 1000-1800;
the auxiliary agent has the structure that:
；
wherein R is 1 Fatty alkanes that are C23;
the preparation method of the composite stabilizer comprises the following steps:
s1, mixing and stirring 1-5 parts by mass of auxiliary stabilizer, 1-5 parts by mass of ultraviolet absorber, 1-15 parts by mass of modified silicon dioxide, 3-9 parts by mass of foaming agent, 20-25 parts by mass of foaming stabilizer and 1-7 parts by mass of filler for 10-20 minutes;
s2, adding 20-50 parts of main stabilizer into the mixture obtained in the step S1, heating to 40-60 ℃, stirring for 30-60 min, and cooling to room temperature to obtain the composite stabilizer;
the preparation method of the auxiliary agent comprises the following steps:
(a) Adding 2, 6-di-tert-butyl p- (dimethylaminomethyl) phenol into a solvent, uniformly stirring, adding 2, 2-bis (bromomethyl) -1, 3-propanediol, heating to a reflux state, and stirring for 24-28 h to obtain a quaternary ammonium salt compound;
(b) Mixing the quaternary ammonium salt compound in the step (a) with wood tar acid, adding an acid regulator to adjust the pH value to 1-6, heating to 60-80 ℃, and stirring for 4-6 hours to obtain an auxiliary agent;
in the step (a), the molar ratio of the 2, 6-di-tert-butyl-p- (dimethylaminomethyl) phenol to the 2, 2-bis (bromomethyl) -1, 3-propanediol is 1 (0.3-0.5);
in the step (b), the molar ratio of the quaternary ammonium salt compound to the pyroligneous acid is 1 (2.2-2.4);
the mass part ratio of the PVC resin to the auxiliary agent is 1 (0.07-0.17).
2. The high temperature and low temperature resistant antimicrobial PVC material according to claim 1, wherein the lubricant is one or more of polyethylene wax, paraffin oil and chlorinated paraffin. .
3. The high temperature and low temperature resistant antimicrobial PVC material according to claim 1, wherein the lubricant is one or more of polyethylene wax, paraffin oil and chlorinated paraffin.
4. A method for preparing the high temperature resistant, low temperature resistant and antibacterial PVC material according to any one of claims 1 to 3, comprising the steps of: and weighing the PVC resin, the composite stabilizer, the lubricant and the auxiliary agent according to the parts by mass, uniformly mixing at 140-160 ℃, and extruding and granulating by a double-screw extruder to obtain the high-temperature-resistant low-temperature-resistant antibacterial PVC material.
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