CN119161636B - A preparation method of PVC composite heat stabilizer, paste resin and building materials - Google Patents
A preparation method of PVC composite heat stabilizer, paste resin and building materials Download PDFInfo
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- CN119161636B CN119161636B CN202411676164.6A CN202411676164A CN119161636B CN 119161636 B CN119161636 B CN 119161636B CN 202411676164 A CN202411676164 A CN 202411676164A CN 119161636 B CN119161636 B CN 119161636B
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- montmorillonite
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- paste resin
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- 239000012760 heat stabilizer Substances 0.000 title claims abstract description 59
- 239000004566 building material Substances 0.000 title claims abstract description 56
- 239000011347 resin Substances 0.000 title claims abstract description 47
- 229920005989 resin Polymers 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical class O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 97
- 239000007788 liquid Substances 0.000 claims abstract description 47
- 238000002156 mixing Methods 0.000 claims abstract description 33
- 238000000227 grinding Methods 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 8
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 239000003063 flame retardant Substances 0.000 claims abstract description 7
- 239000004014 plasticizer Substances 0.000 claims abstract description 7
- 229920000728 polyester Polymers 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 5
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 69
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 68
- 239000006185 dispersion Substances 0.000 claims description 64
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 40
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 34
- 239000001110 calcium chloride Substances 0.000 claims description 34
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 34
- 239000011592 zinc chloride Substances 0.000 claims description 34
- 235000005074 zinc chloride Nutrition 0.000 claims description 34
- 239000002002 slurry Substances 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 235000021355 Stearic acid Nutrition 0.000 claims description 17
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 17
- 239000008117 stearic acid Substances 0.000 claims description 17
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 13
- 239000003921 oil Substances 0.000 claims description 13
- 239000003638 chemical reducing agent Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 102100035474 DNA polymerase kappa Human genes 0.000 claims description 10
- 101710108091 DNA polymerase kappa Proteins 0.000 claims description 10
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- -1 tolylene diphenyl phosphate Chemical compound 0.000 claims description 4
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 3
- 239000008213 purified water Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 3
- 235000011148 calcium chloride Nutrition 0.000 claims description 2
- BJAJDJDODCWPNS-UHFFFAOYSA-N dotp Chemical compound O=C1N2CCOC2=NC2=C1SC=C2 BJAJDJDODCWPNS-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000007581 slurry coating method Methods 0.000 claims 2
- SAOKZLXYCUGLFA-UHFFFAOYSA-N bis(2-ethylhexyl) adipate Chemical compound CCCCC(CC)COC(=O)CCCCC(=O)OCC(CC)CCCC SAOKZLXYCUGLFA-UHFFFAOYSA-N 0.000 claims 1
- 239000002759 woven fabric Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 229910052725 zinc Inorganic materials 0.000 abstract description 8
- 239000011701 zinc Substances 0.000 abstract description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000003381 stabilizer Substances 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 6
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 abstract 1
- 239000007822 coupling agent Substances 0.000 abstract 1
- 230000007547 defect Effects 0.000 abstract 1
- 230000001151 other effect Effects 0.000 abstract 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 168
- 239000004800 polyvinyl chloride Substances 0.000 description 168
- 239000000047 product Substances 0.000 description 41
- 239000004744 fabric Substances 0.000 description 16
- 238000012986 modification Methods 0.000 description 14
- 230000004048 modification Effects 0.000 description 14
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 10
- 238000007598 dipping method Methods 0.000 description 9
- 230000001804 emulsifying effect Effects 0.000 description 9
- 239000012528 membrane Substances 0.000 description 9
- 239000004576 sand Substances 0.000 description 9
- 238000004537 pulping Methods 0.000 description 8
- 230000001105 regulatory effect Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 230000003301 hydrolyzing effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 3
- 239000008116 calcium stearate Substances 0.000 description 3
- 235000013539 calcium stearate Nutrition 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- SPAUYKHQVLTCOL-UHFFFAOYSA-N C1(=CC=CC=C1)OP(OC1=CC=CC=C1)(O)=O.C1(=CC=CC=C1)C Chemical compound C1(=CC=CC=C1)OP(OC1=CC=CC=C1)(O)=O.C1(=CC=CC=C1)C SPAUYKHQVLTCOL-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- OEIWPNWSDYFMIL-UHFFFAOYSA-N dioctyl benzene-1,4-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C=C1 OEIWPNWSDYFMIL-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000006077 pvc stabilizer Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
- C08K2003/162—Calcium, strontium or barium halides, e.g. calcium, strontium or barium chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
- C08K2003/168—Zinc halides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
本发明属于PVC建筑建材技术领域，具体涉及一种PVC复合热稳定剂的制备方法及糊树脂和建材。该PVC复合热稳定剂利用研磨和偶联剂扩层改性钠基蒙脱土，接枝钙锌稳定剂而得，对PVC显示更高的热稳定等作用。该PVC糊树脂采用PVC、增塑剂、PVC复合热稳定剂、液体阻燃剂、抗紫外剂混合搅拌制成，工艺简单易于推广。该PVC建材采用PVC糊树脂调整粘度后与涤纶基材涂层并加热融合而成，具有更好的热稳定性和强度，适于作为建筑建材，利于提高生产效率及产品品质，解决传统稳定剂的“锌烧”等缺陷，并提高建材的热稳定性，降低生产成本。The present invention belongs to the technical field of PVC building materials, and specifically relates to a preparation method of a PVC composite heat stabilizer, a paste resin and a building material. The PVC composite heat stabilizer is obtained by grinding and coupling agent expansion modified sodium montmorillonite, and grafting calcium zinc stabilizer, and has higher thermal stability and other effects on PVC. The PVC paste resin is made by mixing PVC, plasticizer, PVC composite heat stabilizer, liquid flame retardant and anti-ultraviolet agent, and the process is simple and easy to promote. The PVC building material is made by adjusting the viscosity of PVC paste resin, coating with polyester substrate and heating and fusing, and has better thermal stability and strength, is suitable for use as a building material, is conducive to improving production efficiency and product quality, solves the defects of traditional stabilizers such as "zinc burning", and improves the thermal stability of building materials, reducing production costs.
Description
Technical Field
The invention belongs to the technical field of PVC building materials, and particularly relates to a preparation method of a PVC composite heat stabilizer, paste resin and a building material.
Background
Building materials are the most important components of a span space structure and are widely applied to large public facilities such as roof systems of stadiums, airport halls, exhibition centers, platforms, landscape pavilions and the like. Typically such building materials are made from a polyester substrate coated with a PVC (polyvinyl chloride) layer. The PVC building material has the excellent performances of light weight, high strength, flexibility, uniform light transmittance and the like, so the PVC building material has a great development prospect. Because the application scene is outdoor, the thermal stability becomes an important product index, and the addition of the common stabilizer is difficult to achieve the requirement. PVC is of an amorphous structure, has small branching degree, poor light and heat stability, can decompose to generate hydrogen chloride when exposed to sunlight at a temperature of more than 100 ℃ or for a long time, and can be expressed as a large number of bubbles on the surface and in the product in the production process to influence the product quality. In order to ensure normal production, the step-by-step coating needs to be carried out for a small number of times, the production cost is increased, and meanwhile, the quality of the product is unstable.
In order to solve the problem of the stability of PVC building materials, most PVC building material manufacturers choose to add a stabilizer on the original basis, and the stabilizer can prevent the degradation of PVC in the processing and using processes. The traditional stabilizer is mainly used for capturing free radicals generated in the degradation process of PVC, so that further degradation of PVC is prevented. Common PVC heat stabilizers include montmorillonite, stearic acid soap heat stabilizers, and the like. For example, patent document CN109851954A, CN112724558a and the like each adopts a method of mixing a plurality of heat stabilizers as PVC heat stabilizers.
The stability of PVC products and the production process is not changed substantially by adopting the mixed heat stabilizer, and the stability problem still exists. In addition, the PVC dehydrochlorination can be promoted in the action process of the conventionally selected zinc soap salt PVC stabilizer, so that the PVC is degraded in a short time, zinc burning occurs, the production efficiency is reduced, and the environment is polluted.
Disclosure of Invention
Aiming at the problems of poor heat stability and the like of the existing PVC building materials, the invention aims to provide a preparation method of a PVC composite heat stabilizer, paste resin and building materials.
The first aspect provides a preparation method of a PVC composite heat stabilizer, which is prepared from montmorillonite, stearic acid, calcium chloride, zinc chloride and a silane coupling agent, and comprises the following steps:
s1, dispersing and swelling montmorillonite with purified water to obtain montmorillonite dispersion liquid, grinding the montmorillonite dispersion liquid, adding stearic acid during the grinding process, and grinding to obtain pre-modified montmorillonite dispersion liquid;
S2, adding pure water into the silane coupling agent to hydrolyze the silane coupling agent to obtain silane coupling agent liquid, heating the silane coupling agent liquid, adding a calcium chloride/zinc chloride mixture, and blending to obtain a silane coupling agent/calcium chloride/zinc chloride dispersion;
S3, blending a silane coupling agent/calcium chloride/zinc chloride dispersion liquid and a pre-modified montmorillonite dispersion liquid, and heating for reaction to obtain a PVC composite heat stabilizer;
preferably, grinding is carried out in the step S1 until the average grain diameter of montmorillonite is 200-400 nm, the hydrolysis temperature is 20-30 ℃ in the step S2, the hydrolysis time is 2-4 h, the silane coupling agent liquid is heated to 90-100 ℃ in the step S2, the calcium chloride/zinc chloride mixture is added for blending, and the heating reaction temperature is 90-100 ℃ in the step S3, and the reaction time is 2-4 h.
Preferably, the montmorillonite is sodium-based montmorillonite.
Preferably, in the step S1, the feeding amount of the stearic acid is 1-4 times of that of the montmorillonite according to the weight part ratio.
Preferably, in the step S1, the feeding amount of the purified water is 10-20 times of that of montmorillonite according to the weight part ratio;
Preferably, in step S1, the montmorillonite dispersion liquid is prepared by mixing and stirring for 10 min-30 min by an emulsifying machine at a rotation speed of 10000 rpm-20000 rpm.
Preferably, in step S1, the montmorillonite is ground to have an average particle size of 200nm to 300nm.
Preferably, in the step S2, the total feeding amount of the calcium chloride and the zinc chloride is 1-4 times of that of the montmorillonite according to the weight part ratio. Wherein, the calcium chloride and the zinc chloride can be used as commercial blend, and the proportion of the calcium chloride and the zinc chloride belongs to the conventional technology in the field and belongs to the situation which can be changed conventionally.
Preferably, in the step S2, the feeding amount of the silane coupling agent is 0.1-0.4 times of that of montmorillonite according to the weight part ratio.
Preferably, in step S2, the silane coupling agent is at least one of KH550 (γ -aminopropyl triethoxysilane) and KH560 (γ -glycidoxypropyl trimethoxysilane).
In the PVC composite heat stabilizer, when sodium-based montmorillonite is adopted, the montmorillonite has good in-situ polymerization plasticity, expansibility, cation exchange property, dispersibility and thermal stability, and is favorable for grinding, dispersing and modifying. The pure water is used for swelling the montmorillonite, which is beneficial to grinding by a sand mill to reduce the grain size of the montmorillonite and increase the interlayer spacing. In the step S1, stearic acid is utilized for modification while grinding, so that ion exchange reaction is facilitated, hydrogen ions (H +) in stearic acid are easy to replace metal ions between montmorillonite layers, interlayer spacing between montmorillonite layers is increased, specific surface area is increased, activity is enhanced, and stearic acid reacts with montmorillonite to obtain stearic acid modified montmorillonite. The zinc stearate can absorb the byproduct HCl gas in the PVC system, the calcium stearate can inhibit the generation of zinc burning, and the calcium stearate/zinc modified montmorillonite is beneficial to improving the long-term stability of the PVC film. The modification of the silane coupling agent further improves the heat stabilization effect of the heat stabilizer.
In a second aspect, the invention provides a PVC paste resin which can be used for PVC coating of PVC building materials. The PVC paste resin comprises 100 parts by weight of PVC, 30-70 parts by weight of plasticizer, 10-15 parts by weight of liquid flame retardant, 1-3 parts by weight of ultraviolet resistant agent and 1-4 parts by weight of PVC composite heat stabilizer (also called raw material).
Preferably, the preparation method of the PVC paste resin comprises the following steps of mixing PVC, a plasticizer, a liquid flame retardant, an ultraviolet resistant agent and a PVC composite heat stabilizer, and stirring to obtain the PVC paste resin;
preferably, the plasticizer is at least one of DINP (diisononyl phthalate), DOTP (dioctyl terephthalate), DOP (dioctyl phthalate), and DOA (dioctyl adipate);
Preferably, the liquid flame retardant is at least one of tricresyl phosphate, toluene diphenyl phosphate and triphenyl phosphate;
Preferably, the anti-ultraviolet agent can be at least one of UV-531 and UV-9;
In a third aspect, the present invention provides a PVC building material, which can be used as a building material (such as a building membrane material). The building material is prepared from a polyester substrate and a PVC coating, and the preparation method comprises the following steps:
The PVC paste resin is added with a viscosity reducer to adjust the viscosity of the machine to obtain PVC slurry, the PVC slurry and the polyester base material are subjected to dipping and coating by a roller of a coating machine, and the PVC slurry and a PVC film are subjected to heating fusion after the coating is finished to obtain the PVC building material.
Preferably, the viscosity reducer is at least one of D series solvent oils. Further preferred is D80 solvent oil.
Preferably, the on-press viscosity of the PVC slurry is 1000 mpa.s to 2000mpa.s.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the PVC composite heat stabilizer disclosed by the invention, the montmorillonite is subjected to expansion modification through composite modification, and calcium stearate/zinc and silane modification groups are added, so that the heat stabilization effect of the heat stabilizer on PVC can be improved, the generation of HCl gas byproducts is reduced, and the phenomenon of zinc burning generated in the processing process of the traditional metal soap stabilizer is avoided, thereby improving the product quality, reducing the environmental pollution, improving the production efficiency and conforming to the environment-friendly production concept.
(2) The PVC composite heat stabilizer can prevent PVC from degradation in the processing and using processes, so that the service life of the product is prolonged, and the performance and reliability of the product are improved.
(3) The PVC paste resin and the PVC building material have the advantages of simple preparation method, readily available raw materials, reduced production cost of the PVC building material and good economic benefit.
(4) The PVC building material has high stability, excellent physical and chemical properties, such as good flame retardance, high mechanical strength and the like, can be widely applied to industries such as building, medical treatment, electronic appliances and the like, and has wide application prospect;
In general, compared with the prior art, the invention not only improves the product quality and performance of PVC building materials, but also reduces the production cost and environmental pollution, and has obvious superiority.
Detailed Description
The present invention is further described below with reference to specific examples, which are only to be construed as illustrative examples of the technical aspects of the present invention, and are not to be construed as limiting the scope of the present invention.
The materials and sources in the following examples are as follows:
Example 1 preparation of novel PVC composite Heat stabilizer and PVC building Material
The preparation of the novel PVC composite heat stabilizer comprises the following steps:
(1) 5g of sodium montmorillonite and 95g of pure water are fully mixed and emulsified by an emulsifying machine to obtain montmorillonite aqueous dispersion (20 min of stirring at 15000 rpm), so that the montmorillonite is fully swelled. Transferring the obtained montmorillonite aqueous dispersion into a sand mill, grinding for 5 hours at 3500rpm and 60rpm, adding 10g of stearic acid into the system for online modification after grinding for 2 hours, and continuously grinding until the average diameter of montmorillonite particles is 250+/-20 nm to obtain a pre-modified montmorillonite dispersion;
(2) Blending 1gKH550,550 and 2g of pure water, hydrolyzing for 2 hours in a constant-temperature water bath at 25 ℃ to obtain silane coupling agent liquid, heating to 95 ℃, adding 15g of calcium chloride/zinc chloride mixture in an oil bath, and blending for 3 hours to obtain silane coupling agent/calcium chloride/zinc chloride dispersion;
(3) Blending the silane coupling agent/calcium chloride/zinc chloride dispersion liquid obtained in the step (2) and the pre-modified montmorillonite dispersion liquid obtained in the step (1), and reacting for 4 hours under the heating of an oil bath at 97 ℃ to obtain the PVC composite heat stabilizer;
Preparation of PVC building materials:
(1) Mixing and pulping 100g of PVC resin, 40g DINP,10g DOA,3g PVC g of a composite heat stabilizer, 10g of tricresyl phosphate and 1g of UV-531 to obtain PVC paste resin, and regulating the viscosity of the obtained PVC paste resin to 1500mpa.s by using a viscosity reducer D80 to obtain PVC slurry;
(2) And (3) dipping and pasting the PVC slurry and the mesh cloth in the step (1) through a roller of a pasting machine, and fusing the PVC slurry and the mesh cloth at a high temperature of 180 ℃ after pasting to obtain a PVC pasting product (namely, PVC building materials which can be used as PVC building membrane materials).
Example 2 preparation of novel PVC composite Heat stabilizer and PVC building Material
The preparation of the novel PVC composite heat stabilizer comprises the following steps:
(1) 8g of sodium montmorillonite and 92g of pure water are fully mixed and emulsified by an emulsifying machine to obtain montmorillonite aqueous dispersion (20 min of stirring at 15000 rpm), so that the montmorillonite is fully swelled. Transferring the obtained montmorillonite aqueous dispersion into a sand mill, grinding for 5 hours at 3500rpm and 60rpm, adding 10g of stearic acid into the system for online modification after grinding for 2 hours, and continuously grinding until the average diameter of montmorillonite particles is 250+/-20 nm to obtain a pre-modified montmorillonite dispersion;
(2) Blending 1gKH550,550 and 2g of pure water, hydrolyzing for 2 hours in a constant-temperature water bath at 25 ℃ to obtain silane coupling agent liquid, heating to 97 ℃, adding 15g of calcium chloride/zinc chloride mixture in an oil bath, and blending for 1 hour to obtain silane coupling agent/calcium chloride/zinc chloride dispersion;
(3) Blending the silane coupling agent/calcium chloride/zinc chloride dispersion liquid obtained in the step (2) and the pre-modified montmorillonite dispersion liquid obtained in the step (1), and reacting for 4 hours under the heating of an oil bath at 97 ℃ to obtain the PVC composite heat stabilizer;
Preparation of PVC building materials:
(1) Mixing and pulping 100g of PVC resin, 40g of DINP,10g of DOA,3g of PVC composite heat stabilizer, 10g of tricresyl phosphate and 1gUV-531 to obtain PVC paste resin, and regulating the viscosity of the obtained PVC paste resin to 1500mpa.s by using a viscosity reducer D80 to obtain PVC slurry;
(2) And (3) dipping and pasting the PVC slurry and the mesh cloth in the step (1) through a roller of a pasting machine, and fusing the PVC slurry and the mesh cloth at a high temperature of 180 ℃ after pasting to obtain a PVC pasting product (namely, PVC building materials which can be used as PVC building membrane materials).
Example 3 preparation of novel PVC composite Heat stabilizer and PVC building Material
The preparation of the novel PVC composite heat stabilizer comprises the following steps:
(1) 5g of sodium montmorillonite and 95g of pure water are fully mixed and emulsified by an emulsifying machine to obtain montmorillonite aqueous dispersion (20 min of stirring at 15000 rpm), so that the montmorillonite is fully swelled. Transferring the obtained montmorillonite aqueous dispersion into a sand mill, grinding for 5 hours at 3500rpm and 60rpm, adding 15g of stearic acid into the system for online modification after grinding for 2 hours, and continuously grinding until the average diameter of montmorillonite particles is 250+/-20 nm to obtain a pre-modified montmorillonite dispersion;
(2) Blending 1gKH550,550 and 2g of pure water, hydrolyzing for 2 hours in a constant-temperature water bath at 25 ℃ to obtain a silane coupling agent liquid, heating to 95 ℃ and adding 15g of a calcium chloride/zinc chloride mixture to blend for 4 hours in an oil bath to obtain a silane coupling agent/calcium chloride/zinc chloride dispersion;
(3) Blending the silane coupling agent/calcium chloride/zinc chloride dispersion liquid obtained in the step (2) and the pre-modified montmorillonite dispersion liquid obtained in the step (1), and reacting for 4 hours under the heating of an oil bath at 97 ℃ to obtain the PVC composite heat stabilizer;
Preparation of PVC building materials:
(1) Mixing and pulping 100g of PVC resin, 40g of DINP,10g of DOA,3g of PVC composite heat stabilizer, 10g of tricresyl phosphate and 1gUV-531 to obtain PVC paste resin, and regulating the viscosity of the obtained PVC paste resin to 1500mpa.s by using a viscosity reducer D80 to obtain PVC slurry;
(2) And (3) dipping and pasting the PVC slurry and the mesh cloth in the step (1) through a roller of a pasting machine, and fusing the PVC slurry and the mesh cloth at a high temperature of 180 ℃ after pasting to obtain a PVC pasting product (namely, PVC building materials which can be used as PVC building membrane materials).
Example 4 preparation of novel PVC composite Heat stabilizer and PVC building Material
The preparation of the novel PVC composite heat stabilizer comprises the following steps:
(1) 5g of sodium montmorillonite and 95g of pure water are fully mixed and emulsified by an emulsifying machine to obtain montmorillonite aqueous dispersion (stirred for 10min at 20000 rpm) so as to fully swell the montmorillonite. Transferring the obtained montmorillonite aqueous dispersion into a sand mill, grinding for 6 hours at a rotating speed of 3000rpm and a pump speed of 50rpm, adding 10g of stearic acid into the system for online modification after grinding for 3 hours, and continuously grinding until the average diameter of montmorillonite particles is 230+/-20 nm to obtain a pre-modified montmorillonite dispersion;
(2) Blending 2gKH550,550 with 2g of pure water, hydrolyzing for 2 hours in a constant-temperature water bath at 30 ℃ to obtain a silane coupling agent liquid, heating to 95 ℃ and adding 15g of a calcium chloride/zinc chloride mixture to blend for 2 hours in an oil bath to obtain a silane coupling agent/calcium chloride/zinc chloride dispersion;
(3) Blending the silane coupling agent/calcium chloride/zinc chloride dispersion liquid obtained in the step (2) and the pre-modified montmorillonite dispersion liquid obtained in the step (1), and reacting for 2 hours under the heating of an oil bath at the temperature of 95 ℃ to obtain the PVC composite heat stabilizer;
Preparation of PVC building materials:
(1) Mixing and pulping 100g of PVC resin, 40g of DINP,10g of DOA,2g of PVC composite heat stabilizer, 10g of tricresyl phosphate and 1gUV-531 to obtain PVC paste resin, and regulating the viscosity of the obtained PVC paste resin to 1500mpa.s by using a viscosity reducer D80 to obtain PVC slurry;
(2) And (3) dipping and pasting the PVC slurry and the mesh cloth in the step (1) through a roller of a pasting machine, and fusing the PVC slurry and the mesh cloth at a high temperature of 180 ℃ after pasting to obtain a PVC pasting product (namely, PVC building materials which can be used as PVC building membrane materials).
Example 5 preparation of novel PVC composite Heat stabilizer and PVC building Material
The preparation of the novel PVC composite heat stabilizer comprises the following steps:
(1) 5g of sodium montmorillonite and 75g of pure water are fully mixed and emulsified by an emulsifying machine to obtain montmorillonite aqueous dispersion (the montmorillonite aqueous dispersion is mixed and stirred for 30min at the rotating speed of 10000 rpm) so as to fully swell the montmorillonite. Transferring the obtained montmorillonite aqueous dispersion into a sand mill, grinding for 4 hours at the rotation speed of 4000rpm and the pump speed of 80rpm, adding 20g of stearic acid into the system for online modification after grinding for 2 hours, and continuously grinding until the average diameter of montmorillonite particles is 270+/-20 nm to obtain a pre-modified montmorillonite dispersion;
(2) Blending 1gKH550,550 and 2g of pure water, hydrolyzing for 4 hours in a constant-temperature water bath at 20 ℃ to obtain a silane coupling agent liquid, heating to 92 ℃, and adding 20g of a calcium chloride/zinc chloride mixture to blend for 4 hours to obtain a silane coupling agent/calcium chloride/zinc chloride dispersion;
(3) Blending the silane coupling agent/calcium chloride/zinc chloride dispersion liquid obtained in the step (2) and the pre-modified montmorillonite dispersion liquid obtained in the step (1), and reacting for 4 hours under the heating of 90 ℃ oil bath to obtain the PVC composite heat stabilizer;
Preparation of PVC building materials:
(1) Mixing and pulping 100g of PVC resin, 40g of DINP,30g of DOA,4g of PVC composite heat stabilizer, 15g of triphenyl phosphate and 3gUV-531 to obtain PVC paste resin, and regulating the viscosity of the obtained PVC paste resin to 2000mpa.s by using a viscosity reducer D80 to obtain PVC slurry;
(2) And (3) dipping and pasting the PVC slurry and the mesh cloth in the step (1) through a roller of a pasting machine, and fusing the PVC slurry and the mesh cloth at a high temperature of 180 ℃ after pasting to obtain a PVC pasting product (namely, PVC building materials which can be used as PVC building membrane materials).
Comparative example 1 preparation of novel PVC composite Heat stabilizer and PVC building Material
Preparation of PVC heat stabilizer:
(1) 5g of sodium montmorillonite and 95g of pure water are fully mixed and emulsified by an emulsifying machine to obtain montmorillonite aqueous dispersion (20 min of stirring at 15000 rpm), so that the montmorillonite is fully swelled. Transferring the obtained montmorillonite aqueous dispersion into a sand mill, grinding for 5 hours at 3500rpm and 60rpm, grinding until the average diameter of montmorillonite particles is 250+/-20 nm, obtaining montmorillonite dispersion liquid, and adding 15g of calcium chloride/zinc chloride mixture into the montmorillonite dispersion liquid to obtain mixed heat stabilizer dispersion liquid.
Preparation of PVC building materials:
(1) Mixing 100g of PVC resin, 40g DINP,10g DOA,3g g of heat stabilizer dispersion liquid, 10g of tricresyl phosphate and 1g of UV-531, and pulping to obtain PVC paste resin, and regulating the viscosity of the obtained PVC paste resin to 1500mpa.s by using a viscosity reducer D80 to obtain PVC slurry;
(2) And (3) dipping and pasting the PVC slurry and the mesh cloth in the step (1) through a roller of a pasting machine, and fusing the PVC slurry and the mesh cloth at a high temperature of 180 ℃ after pasting to obtain a PVC pasting product (namely, PVC building materials which can be used as PVC building membrane materials).
Comparative example 2 preparation of novel PVC composite Heat stabilizer and PVC building Material
Preparation of PVC heat stabilizer:
(1) 5g of sodium montmorillonite and 95g of pure water are fully mixed and emulsified by an emulsifying machine to obtain montmorillonite aqueous dispersion (20 min of stirring at 15000 rpm), so that the montmorillonite is fully swelled. Transferring the obtained montmorillonite aqueous dispersion into a sand mill, grinding for 5 hours at 3500rpm and 60rpm, adding 10g of stearic acid into the system for online modification after grinding for 2 hours, continuously grinding until the average diameter of montmorillonite particles is 250+/-20 nm to obtain modified montmorillonite dispersion liquid, and adding 15g of calcium chloride/zinc chloride mixture into the modified montmorillonite dispersion liquid to obtain mixed heat stabilizer dispersion liquid.
Preparation of PVC building materials:
(1) Mixing 100g of PVC resin, 40g DINP,10g DOA,3g g of heat stabilizer dispersion liquid, 10g of tricresyl phosphate and 1g of UV-531, and pulping to obtain PVC paste resin, and regulating the viscosity of the obtained PVC paste resin to 1500mpa.s by using a viscosity reducer D80 to obtain PVC slurry;
(2) And (3) dipping and pasting the PVC slurry and the mesh cloth in the step (1) through a roller of a pasting machine, and fusing the PVC slurry and the mesh cloth at a high temperature of 180 ℃ after pasting to obtain a PVC pasting product (namely, PVC building materials which can be used as PVC building membrane materials).
Comparative example 3 preparation of novel PVC composite Heat stabilizer and PVC building Material
Preparation of PVC heat stabilizer:
(1) 5g of sodium montmorillonite and 95g of pure water are fully mixed and emulsified by an emulsifying machine to obtain montmorillonite aqueous dispersion (20 min of stirring at 15000 rpm), so that the montmorillonite is fully swelled. Transferring the obtained montmorillonite aqueous dispersion into a sand mill, grinding for 5 hours at 3500rpm and 60rpm, and grinding until the average diameter of montmorillonite particles is 250+ -20 nm to obtain montmorillonite dispersion;
(2) Mixing 1gKH550,550 with 2g of pure water, hydrolyzing for 2 hours in a constant-temperature water bath at 25 ℃ to obtain a silane coupling agent liquid, heating to 95 ℃, and adding 15g of a calcium chloride/zinc chloride mixture for mixing to obtain a silane coupling agent/calcium chloride/zinc chloride dispersion;
(3) Blending the silane coupling agent/calcium chloride/zinc chloride dispersion liquid obtained in the step (2) with the montmorillonite dispersion liquid obtained in the step (1), and reacting for 4 hours under the heating of an oil bath at 97 ℃ to obtain a silane coupling agent modified montmorillonite dispersion liquid;
Preparation of PVC building materials:
(1) Mixing and pulping 100g of PVC resin, 40g DINP,10g DOA,3g g of silane coupling agent modified montmorillonite dispersion liquid, 10g of tricresyl phosphate and 1g of UV-531 to obtain PVC paste resin, and regulating the viscosity of the obtained PVC paste resin to 1500mpa.s by using a viscosity reducer D80 to obtain PVC slurry;
(2) And (3) dipping and pasting the PVC slurry and the mesh cloth in the step (1) through a roller of a pasting machine, and fusing the PVC slurry and the mesh cloth at a high temperature of 180 ℃ after pasting to obtain a PVC pasting product (namely, PVC building materials which can be used as PVC building membrane materials).
Product performance measurement:
The product properties were measured for the products of examples 1-5 and comparative examples 1-3, and the measurement conditions were the same.
The bubble condition was observed using a polarized light microscope:
The method for testing the bubble condition on the surface of the product comprises the steps of adjusting focal length under the visual field of 10 times of an ocular lens and 5 times of an objective lens until the inside of the product shows blurring, and observing the bubble condition on the surface of the product when the surface of the product shows clear;
The method for testing the bubble condition in the product comprises the steps of adjusting focal length under the visual field of 10 times of an ocular lens and 5 times of an objective lens until the internal appearance of the product is clear, and observing the bubble condition on the surface of the product by blurring the surface appearance of the product;
Bubble number characterization criteria-one "+" for every 50 bubbles in a 0.5 x 0.5mm field of view "
TABLE 1 polarized light microscope observes bubble condition (surface and interior) of product
And (3) simulating ultraviolet aging product performance test:
setting ultraviolet aging box conditions according to ASTM G154 cycle1 standard, performing test for 2500 hours in total, and comparing the test sample with the original sample to obtain 2500 hours of simulated ultraviolet aging product color value;
Table 2 2500h simulation ultraviolet aged product color values (Lab color model)
And (3) testing the mechanical properties of the product:
according to the national standard of GB-T10401, the mechanical property of the product is tested by using a peeling strength tester, a tensile strength tester and a tearing strength tester.
Table 3 mechanical properties of example products
Table 1 shows that the bubbles of examples 1-5 are significantly reduced in the case of each sample under the polarizing microscope, indicating that the HCl gas byproduct generation of the present product is significantly suppressed, the thermal stability is improved, the product quality is improved, and the "zinc burn" phenomenon of the conventional product is significantly improved. Table 2 shows the color difference results of the ultraviolet aging test for each sample, and the color difference of the products of examples 1-5 is smaller than that of the comparative example, which shows that the ultraviolet aging resistance of the product is greatly improved, and the product is more suitable for PVC building materials. Table 3 shows that the peel strength, tensile strength, and tear strength of each sample are better than those of the comparative examples 1-5.
The above description of the embodiments is only for aiding in the understanding of the method of the present invention and its core ideas. It should be noted that it will be apparent to those skilled in the art that several improvements and modifications can be made to the present invention without departing from the basic principles of the invention, and these improvements and modifications will fall within the scope of the claims. The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
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