CN111548747B - Self-adhesive polyvinyl chloride waterproof coiled material - Google Patents
Self-adhesive polyvinyl chloride waterproof coiled material Download PDFInfo
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- CN111548747B CN111548747B CN202010426905.0A CN202010426905A CN111548747B CN 111548747 B CN111548747 B CN 111548747B CN 202010426905 A CN202010426905 A CN 202010426905A CN 111548747 B CN111548747 B CN 111548747B
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- polyvinyl chloride
- crosslinking
- added
- reaction kettle
- flexibilizer
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- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 127
- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 127
- 239000000853 adhesive Substances 0.000 title claims abstract description 20
- 239000000463 material Substances 0.000 title claims abstract description 20
- 238000004132 cross linking Methods 0.000 claims abstract description 64
- 239000012745 toughening agent Substances 0.000 claims abstract description 30
- 238000002360 preparation method Methods 0.000 claims abstract description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- 239000011888 foil Substances 0.000 claims abstract description 8
- 230000001070 adhesive effect Effects 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 55
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000013067 intermediate product Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- -1 acetyl unsaturated acid diethyl ester Chemical class 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 13
- 238000002390 rotary evaporation Methods 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 10
- HAZRIBSLCUYMQP-UHFFFAOYSA-N 1,2-diaminoguanidine;hydron;chloride Chemical compound Cl.NN\C(N)=N/N HAZRIBSLCUYMQP-UHFFFAOYSA-N 0.000 claims description 9
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 8
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 7
- OZZYKXXGCOLLLO-TWTPFVCWSA-N ethyl (2e,4e)-hexa-2,4-dienoate Chemical compound CCOC(=O)\C=C\C=C\C OZZYKXXGCOLLLO-TWTPFVCWSA-N 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- HFLMYYLFSNEOOT-UHFFFAOYSA-N methyl 4-chloro-3-oxobutanoate Chemical compound COC(=O)CC(=O)CCl HFLMYYLFSNEOOT-UHFFFAOYSA-N 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims 3
- 238000004078 waterproofing Methods 0.000 claims 3
- 238000004513 sizing Methods 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 40
- 238000002425 crystallisation Methods 0.000 abstract description 5
- 230000008025 crystallization Effects 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 34
- 238000010521 absorption reaction Methods 0.000 description 13
- 239000004014 plasticizer Substances 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 239000012760 heat stabilizer Substances 0.000 description 9
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 9
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 8
- 238000005979 thermal decomposition reaction Methods 0.000 description 8
- 125000003277 amino group Chemical group 0.000 description 7
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 229910018557 Si O Inorganic materials 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 5
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 4
- 229920006037 cross link polymer Polymers 0.000 description 4
- 229910021419 crystalline silicon Inorganic materials 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000007942 carboxylates Chemical class 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 125000006414 CCl Chemical group ClC* 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000007033 dehydrochlorination reaction Methods 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 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 description 1
- DAWJJMYZJQJLPZ-UHFFFAOYSA-N 2-sulfanylprop-2-enoic acid Chemical compound OC(=O)C(S)=C DAWJJMYZJQJLPZ-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229940124543 ultraviolet light absorber Drugs 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/245—Vinyl resins, e.g. polyvinyl chloride [PVC]
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1876—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/548—Silicon-containing compounds containing sulfur
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/262—Alkali metal carbonates
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/10—Presence of inorganic materials
- C09J2400/16—Metal
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2427/00—Presence of halogenated polymer
- C09J2427/006—Presence of halogenated polymer in the substrate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a self-adhesive polyvinyl chloride waterproof coiled material which comprises a polyvinyl chloride sheet and an aluminum foil layer, wherein the polyvinyl chloride sheet and the aluminum foil layer are bonded through an adhesive. According to the waterproof coiled material, the toughening and modification of the polyvinyl chloride are realized through the crosslinking toughening agent in the preparation process, the crosslinking toughening agent contains two sulfydryl groups, the two sulfydryl groups are positioned in two different directions, the two sulfydryl groups can respectively react between two polyvinyl chloride molecular chains, so that the polyvinyl chloride molecular chains are connected through the crosslinking toughening agent to form a net-shaped crosslinking structure, the distance between the two polyvinyl chloride molecules is increased through the interval of the crosslinking toughening agent, the polyvinyl chloride molecules cannot be combined through intermolecular force, the crystallization degree of the polyvinyl chloride molecules is reduced, the molecular chains of the crosslinking toughening agent are connected through a large number of flexible groups, the toughness between the polyvinyl chloride molecules is improved, and the strength of a polymer is improved through the crosslinking effect.
Description
Technical Field
The invention belongs to the field of waterproof coiled material preparation, and relates to a self-adhesive polyvinyl chloride waterproof coiled material.
Background
Polyvinyl chloride is widely applied to the preparation of waterproof rolls due to low cost, excellent hydrophobicity, flame retardant property and chemical resistance, but polyvinyl chloride molecules are easy to agglomerate and crystallize due to intermolecular force, so that the toughness of the rolls is influenced.
Meanwhile, polyvinyl chloride generates free radicals under the action of ultraviolet rays and heat, and the polymer is subjected to dehydrochlorination under the induction of the free radicals, while the dehydrochlorination can accelerate the generation of the free radicals and further accelerate the decomposition of the polymer, so that the polymer is easy to form chain-type catalysis action through hydrogen chloride gas, which is easy to cause polymer oxidative fracture and further reduce the strength of the polymer, in the prior art, a heat stabilizer is directly added into the polymer, because the compatibility between the heat stabilizer and the polyvinyl chloride polymer is lower, the dispersion of the heat stabilizer is easy to cause nonuniform dispersion to influence the thermal stability of the polymer, meanwhile, when the heat stabilizer is added alone, the ultraviolet action is easy to cause the oxidation of the polymer, and when the heat stabilizer and an ultraviolet absorbent are added simultaneously, the slight thermal decomposition still exists, and a small amount of ultraviolet can also act on the, the anti-aging effect cannot be fully achieved.
Disclosure of Invention
The invention aims to provide a self-adhesive polyvinyl chloride waterproof coiled material, wherein the preparation process of the waterproof coiled material realizes toughening modification of polyvinyl chloride through a crosslinking toughening agent, the crosslinking toughening agent contains two sulfydryl groups which are positioned in two different directions, the two sulfydryl groups can respectively react between two polyvinyl chloride molecular chains, so that the polyvinyl chloride molecular chains are connected through the crosslinking toughening agent to form a reticular crosslinking structure, the distance between the two polyvinyl chloride molecules is increased through the interval of the crosslinking toughening agent, the connected polyvinyl chloride molecules cannot be combined through intermolecular force, the crystallization degree of the polyvinyl chloride molecules is reduced, and the crosslinking toughening agent molecular chains are connected through a large amount of flexible groups such as C-N bonds, C-Si bonds, C-O bonds and Si-O bonds, the toughness between polyvinyl chloride molecules is improved, although the molecular distance is increased, the two adjacent polyvinyl chloride molecules are connected through the crosslinking flexibilizer, but the strength of the polyvinyl chloride materials cannot be reduced but is increased, so that the toughness and the strength of the polyvinyl chloride materials can be improved without adding any plasticizer in the use process of the polyvinyl chloride, and the problems that in the prior art, the plasticizer is usually added into the polyvinyl chloride, the acting force between the polyvinyl chloride molecules is weakened through the intermolecular acting force between the plasticizer and the polyvinyl chloride, the flexibility of the polyvinyl chloride molecules is effectively prevented from being improved, but the plasticizer is easy to migrate at a higher temperature, and when the adding content of the plasticizer is higher, the flexibility of the polyvinyl chloride polymers is increased, and the strength of the polyvinyl chloride polymers is easy to reduce are solved.
The purpose of the invention can be realized by the following technical scheme:
a self-adhesive polyvinyl chloride waterproof coiled material comprises a polyvinyl chloride sheet and an aluminum foil layer, wherein the polyvinyl chloride sheet and the aluminum foil layer are bonded through a waterproof bonding layer, and when the self-adhesive polyvinyl chloride waterproof coiled material is used, the aluminum foil layer is directly torn off, and the waterproof coiled material can be bonded through the waterproof bonding layer;
preferably, the polyvinyl chloride sheet is prepared as follows:
firstly, adding polyvinyl chloride powder, a crosslinking flexibilizer, sodium carbonate and cyclohexanone into a reaction kettle at the same time, heating to 80-90 ℃, carrying out reflux reaction for 35-38h, then carrying out rotary evaporation to recover a solvent, and washing and drying a solid obtained after the rotary evaporation by using water and acetone in sequence to obtain crosslinking modified polyvinyl chloride powder; because the prepared crosslinking flexibilizer contains two sulfydryl groups which are positioned in two different directions, the two sulfydryl groups can respectively react between two polyvinyl chloride molecular chains, so that the polyvinyl chloride molecular chains are connected through the crosslinking flexibilizer to form a reticular crosslinking structure, because the distance between the two polyvinyl chloride molecules is increased through the interval of the crosslinking flexibilizer, the connected polyvinyl chloride molecules cannot be combined through intermolecular force, the crystallization degree of the polyvinyl chloride molecules is reduced, and because the molecular chains of the crosslinking flexibilizer are connected through a large number of flexible groups such as C-N bonds, C-Si bonds, C-O bonds and Si-O bonds, the toughness between the polyvinyl chloride molecules is improved, although the molecular distance is increased, because the two adjacent polyvinyl chloride molecules are connected through the crosslinking flexibilizer, but the strength of the polyvinyl chloride material can not be reduced but increased, so that the toughness and the strength of the polyvinyl chloride material can be improved without adding any plasticizer in the use process of the polyvinyl chloride, meanwhile, because the crosslinking flexibilizer contains 2, 4-dihydroxybenzophenone, a large number of amino and siloxane bonds, and the nodes of the crosslinked polymer network structure all contain the 2, 4-dihydroxybenzophenone and the large number of amino and siloxane bonds, the 2, 4-dihydroxybenzophenone is uniformly dispersed in the crosslinked polymer, thereby effectively realizing the comprehensive adsorption of ultraviolet rays acting on the surface of the polymer, simultaneously, because the amino groups contain a large number, hydrogen chloride released by the oxidative decomposition of the polymer is instantly adsorbed by the amino groups, the catalytic action of the hydrogen chloride on the oxidation of the polymer is reduced, and simultaneously, because the polymer network structure evenly contains a large number of siloxane bonds, the high temperature resistance of the polymer is improved, the high temperature resistance strength of the prepared polymer is increased, the occurrence of thermal decomposition can be effectively prevented, any heat stabilizer does not need to be added in the preparation process of the polymer, and the problem of reduced thermal stability caused by uneven dispersion of the added heat stabilizer can be effectively prevented;
and secondly, adding the crosslinked modified polyvinyl chloride powder and the calcium carbonate into an open mill simultaneously for melting and plasticizing, then discharging sheets, preheating the sheets in a vulcanizing machine at 180 ℃ for 10-15min, pressurizing, exhausting, maintaining pressure for 5-7min, and then shaping by a cold press to obtain the polyvinyl chloride sheets.
Preferably, 328g of crosslinking toughening agent 316-.
Preferably, 90-95g of calcium carbonate is added to every kilogram of the crosslinked and modified polyvinyl chloride powder in the second step;
preferably, the specific preparation process of the crosslinking flexibilizer is as follows:
step 1, weighing a certain amount of methyl 4-chloroacetoacetate, ethyl sorbate, ethanol and sodium ethoxide, simultaneously adding into a reaction kettle, heating to 70-100 ℃, carrying out reflux reaction for 3-4h, washing the product with deionized water for 4-5 times, drying and filtering with anhydrous sodium sulfate, carrying out reduced pressure distillation on the filtrate, and collecting 145-149 ℃ (2.27KPa) to obtain diethyl acetyl unsaturated acid; under the alkaline condition, the active hydrogen on the carbonyl ortho-position methyl in the 4-chloroacetoacetic acid methyl ester can be abstracted by alkali to form carbanions, and the carbanions can perform conjugate addition reaction with unsaturated carbonyl due to the fact that the carbonyl in the sorbic acid ethyl ester contains conjugated olefin groups;
step 2: simultaneously adding acetyl unsaturated diethyl acetate and anhydrous acetone into a reaction kettle, simultaneously adding a platinum catalyst into the reaction kettle, continuously introducing nitrogen into the reaction kettle, simultaneously heating to 100-105 ℃, dropwise adding trimethoxy hydrosilane into the reaction kettle, controlling the reaction kettle to react for 3-4 hours at constant temperature after the dropwise adding is completed within 30min, then cooling to room temperature, removing the solvent and unreacted trimethoxy hydrosilane by rotary evaporation, repeatedly washing the product with water, and drying to obtain silanized acetyl unsaturated diethyl acetate;
and step 3: adding 2, 4-dihydroxybenzophenone into ethanol, stirring for dissolving, then adding solid caustic soda, heating to 75-80 ℃ after stirring for dissolving, then slowly dropwise adding silanized acetyl unsaturated acid diethyl ester into the reaction kettle, controlling the dropwise adding to be complete within 30min, carrying out constant-temperature reflux reaction for 6-7h after the dropwise adding is complete, and then carrying out filtering, washing and drying to obtain an intermediate product M1;
and 4, step 4: adding the intermediate product M1 and acetone into a reaction kettle, stirring and dissolving, dropwise adding sodium hydroxide to control the pH value of the solution to be 13, then adding 1, 3-diaminoguanidine hydrochloride into the reaction kettle, stirring and reacting at normal temperature for 3-4h, washing the product solution with deionized water, then layering to obtain an oil phase, drying the oil phase with anhydrous sodium sulfate, and then carrying out reduced pressure distillation to obtain an intermediate product M2; the 1, 3-diaminoguanidine hydrochloride contains primary amino groups, has high activity, can perform addition reaction with unsaturated conjugated alkenyl ester under alkaline conditions, and introduces two 1, 3-diaminoguanidine hydrochloride into the intermediate product M1 by controlling the addition content ratio between the 1, 3-diaminoguanidine hydrochloride and the intermediate product M1, so that the intermediate product M2 contains a large amount of amino groups;
and 5: mixing an intermediate product M2 and acetone according to a mass ratio of 1:1 to prepare a solution, then simultaneously adding 3-mercaptopropionic acid and thionyl chloride into a reaction container, heating to 60-65 ℃, carrying out reflux reaction for 2-3h, then reducing the temperature to room temperature, adding the prepared intermediate product M2 solution and triethylamine, stirring and reacting for 4-5h, then carrying out rotary evaporation to remove a solvent and unreacted micromolecule substances, adding the evaporated product into water, and washing off generated salt to obtain a crosslinking flexibilizer; two sulfydryl groups are introduced into the prepared crosslinking toughening agent by controlling the proportion of 3-mercaptopropionic acid and the intermediate product M2, the two sulfydryl groups are positioned in different directions, and meanwhile, the intermediate product M2 contains a large amount of amino groups, so that the prepared crosslinking toughening agent contains a large amount of amino groups, the absorption of hydrogen chloride can be realized, and meanwhile, the introduced siloxane bond can improve the high-temperature resistance of the crosslinking toughening agent;
preferably, 945-950g of ethyl sorbate, 4.6-4.7L of ethanol and 210-215g of sodium ethoxide are added in each kg of methyl 4-chloroacetoacetate in the step 1;
preferably, 440-446g of trimethoxyhydrosilane, 10.6-11.2g of platinum catalyst and 2.7-2.8L of anhydrous acetone are added into each kilogram of acetyl unsaturated acid diethanol in the step 2;
preferably, in step 3, 1.95-1.96kg of silanized acetyl unsaturated diethyl ester is added into each kg of 2, 4-dihydroxybenzophenone, 620-625g of solid caustic soda is added, and 3.2-3.3L of ethanol is added;
preferably, in step 4, 410-415g of 1, 3-diaminoguanidine hydrochloride are added per kg of intermediate M1;
preferably, in step 5, per kg of intermediate M2, 140-145g of 3-mercaptopropionic acid, 180-186g of thionyl chloride and 400-410g of triethylamine are added.
The invention has the beneficial effects that:
1. the waterproof coiled material realizes toughening modification of polyvinyl chloride through the crosslinking toughening agent in the preparation process, the crosslinking toughening agent contains two sulfydryl groups, the two sulfydryl groups are positioned in two different directions, the two sulfydryl groups can respectively react between two polyvinyl chloride molecular chains, so that the polyvinyl chloride molecular chains are connected through the crosslinking toughening agent to form a net-shaped crosslinking structure, the distance between the two polyvinyl chloride molecules is increased through the interval of the crosslinking toughening agent, the connected polyvinyl chloride molecules cannot be combined through intermolecular force, the crystallization degree of the polyvinyl chloride molecules is reduced, and the toughness among the polyvinyl chloride molecules is improved because the molecular chains of the crosslinking toughening agent are connected through a large number of flexible groups, namely C-N bonds, C-Si bonds, C-O bonds and Si-O bonds, although the molecular distance is increased, the two adjacent polyvinyl chloride molecules are connected through the crosslinking flexibilizer, but the strength of the polyvinyl chloride materials is not reduced but is increased, so that the toughness and the strength of the polyvinyl chloride materials can be improved without adding any plasticizer in the use process of the polyvinyl chloride, and the problems that in the prior art, the acting force between the polyvinyl chloride molecules is weakened through the intermolecular acting force between the plasticizer and the polyvinyl chloride, the flexibility of the polyvinyl chloride molecules is effectively prevented from being improved, but the plasticizer is easy to migrate at a higher temperature, and when the adding content of the plasticizer is higher, the strength of the polyvinyl chloride polymers is easy to reduce while the flexibility of the polyvinyl chloride polymers is improved are solved.
2. According to the invention, siloxane bonds are introduced into the crosslinking flexibilizer, so that after the crosslinking flexibilizer forms a net structure in crosslinking modified polyvinyl chloride, the siloxane bonds are uniformly distributed on the net structure of the polymer, the high temperature resistance of the polymer is improved, the high temperature resistance strength of the prepared polymer is increased, the occurrence of thermal decomposition can be effectively prevented, any heat stabilizer does not need to be added in the preparation process of the polymer, and the problem of reduced thermal stability caused by nonuniform dispersion of the added heat stabilizer can be effectively prevented.
3. The crosslinking flexibilizer prepared by the invention contains 2, 4-dihydroxybenzophenone, a large amount of amino and siloxane bonds, and the nodes of the network structure of the crosslinked polymer all contain the 2, 4-dihydroxybenzophenone, a large amount of amino and siloxane bonds, so that the 2, 4-dihydroxybenzophenone is uniformly dispersed in the crosslinked polymer, the comprehensive adsorption of ultraviolet rays acting on the surface of the polymer is effectively realized, the thermal decomposition of polyvinyl chloride is effectively prevented, the aging action of light and heat on the polyvinyl chloride is prevented, even if the thermal stability and the slight thermal decomposition action of the polymer after ultraviolet absorption still exist, and a small amount of ultraviolet rays can also act on the polymer after absorption, but because of the large amount of amino, the hydrogen chloride released by the small amount of oxidative decomposition of the polymer is instantly adsorbed by the amino, and the catalytic action of the hydrogen chloride on the polymer oxidation can also be prevented, and high-efficiency ageing resistance is realized.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
Examples and comparative examples of (first) crosslinked tougheners preparation methods:
example 1:
the preparation process of the crosslinking flexibilizer comprises the following steps:
step 1, weighing 150g of 4-methyl chloroacetoacetate, 142g of ethyl sorbate, 700mL of ethanol and 32g of sodium ethoxide, simultaneously adding the materials into a reaction kettle, heating to 70 ℃, carrying out reflux reaction for 4 hours, washing the product with deionized water for 4-5 times, drying and filtering the product with anhydrous sodium sulfate, carrying out reduced pressure distillation on the filtrate, collecting 145-149 ℃ (2.27KPa) to obtain diethyl acetyl unsaturated acid, carrying out infrared characterization on the diethyl acetyl unsaturated acid, and 763cm-1The peak of C-Cl stretching vibration appears at the same time of 1684cm-1The absorption peak of C ═ C, 1732cm-1An absorption peak of the ester group appears;
step 2: 290g of acetyl unsaturated diethyl acetate and 800mL of anhydrous acetone are simultaneously added into a reaction kettle, 3.1g of platinum catalyst PT-4000 is simultaneously added into the reaction kettle, nitrogen is continuously introduced into the reaction kettle, the temperature is simultaneously increased to 105 ℃, 128g of trimethoxy hydrosilane is dropwise added into the reaction kettle, the constant temperature reaction is carried out for 4 hours after the complete dropwise addition is controlled within 30 minutes, the temperature is reduced to room temperature, the solvent and the unreacted trimethoxy hydrosilane are removed through rotary evaporation, the product is repeatedly washed by water and dried to obtain silanized acetyl unsaturated diethyl acetate, the reaction formula is shown as follows, the silanized acetyl unsaturated diethyl acetate is subjected to infrared analysis, and the infrared analysis is carried out at 1083cm-1An absorption peak of Si-O bond appears;
and step 3: adding 214g2, 4-dihydroxybenzophenone into 700mL ethanol, stirring for dissolving, adding 133g solid caustic soda, stirring for dissolving, heating to 75 ℃, slowly adding 418g silanized diethyl acetyl unsaturated acid dropwise into the reaction kettle, and controlling the dropwise addition within 30minAnd (3) completely dropwise adding, carrying out constant-temperature reflux reaction for 7h, filtering, washing and drying to obtain an intermediate product M1, wherein the reaction formula is shown as follows, and infrared analysis is carried out on the intermediate product M1 at 763cm-1The absorption peak at C-Cl disappeared at the same time as 1690-1An infrared absorption peak of carbonyl between two benzene rings appears;
and 4, step 4: adding 63g of intermediate product M1 and 300mL of acetone into a reaction kettle, stirring and dissolving, dropwise adding sodium hydroxide to control the pH value of the solution to be 13, then adding 26g of 1 and 3-diaminoguanidine hydrochloride into the reaction kettle, stirring and reacting for 4h at normal temperature, washing the product solution with deionized water, then layering to obtain an oil phase, drying the oil phase through anhydrous sodium sulfate, and then carrying out reduced pressure distillation to obtain an intermediate product M2, wherein the reaction formula is shown as follows, and the infrared analysis is carried out on M2, and 1732cm is carried out-1The absorption peak of the ester group at the time of treatment disappeared at 3363cm-1And 3210cm-1With primary amine C-NH2Double absorption peak of (a);
and 5: mixing an intermediate product M2 and acetone according to a mass ratio of 1:1 to prepare a solution, then simultaneously adding 106g of 3-mercaptopropionic acid and 135g of thionyl chloride into a reaction container, heating to 60 ℃, carrying out reflux reaction for 3 hours, then reducing the temperature to room temperature, adding 1.5kg of the prepared intermediate product M2 solution and 300g of triethylamine, stirring for reaction for 5 hours, then carrying out rotary evaporation to remove the solvent and unreacted small molecular substances, adding the evaporated product into water to wash off the generated salt to obtain a crosslinking flexibilizer, wherein the reaction formula is shown in the specification, then carrying out infrared analysis on a product B, and 2528cm-1An absorption peak of-S-H appears;
comparative example 1:
the specific preparation process of the crosslinking flexibilizer is the same as that of example 1, wherein the preparation process of silanized diethyl acetyl unsaturated carboxylate in step 2 is omitted, and the silanized diethyl acetyl unsaturated carboxylate prepared in step 2 used in step 3 is directly replaced by the diethyl acetyl unsaturated carboxylate prepared in step 1.
Comparative example 2:
the preparation process of the crosslinking flexibilizer comprises the following steps:
step 1, step 2 and step 3 were the same as in example 1;
and 4, step 4: adding 63g of intermediate product M1 and 200mL of toluene into a reaction kettle, stirring and dissolving, then adding 23g of 1, 4-butanediol, heating to 120 ℃, dropwise adding 10g of sodium ethoxide, distilling off ethanol, keeping the distillation temperature not more than 90 ℃, continuing to distill off ethanol after the sodium ethoxide is completely dropwise added, and then decompressing and recovering the unreacted 1, 4-butanediol and the solvent to obtain an intermediate product A1;
and 5: adding 100g of intermediate product A and 200mL of acetone into a reaction kettle, stirring and dissolving, then adding 34g of 3-mercaptopropionic acid, 6g of concentrated sulfuric acid and 3g of 3A molecular sieve, heating to 95 ℃, carrying out reflux reaction for 3-4h, then cooling, filtering and recovering the 3A molecular sieve, then dropwise adding ammonia water until reactants are neutral, carrying out rotary evaporation to remove solvents of acetone, ammonia water and unreacted 3-mercaptopropionic acid, then washing the obtained solid product for 4-5 times by using water, and drying to obtain the crosslinking flexibilizer.
Comparative example 3:
the specific preparation process of the toughening agent modifier is the same as that of the embodiment 1, the ethyl sorbate used in the first step in the embodiment 1 is replaced by crotonaldehyde, only one ester group is contained in the prepared product, only one 1, 3-diaminoguanidine hydrochloride can be introduced, and one sulfydryl is introduced into the prepared toughening agent through the reaction of the 1, 3-diaminoguanidine hydrochloride and mercaptoacrylic acid.
Examples and comparative examples of the Process for producing (II) polyvinyl chloride sheet
Example 2:
the preparation process of the polyvinyl chloride sheet is as follows:
step one, adding 1kg of polyvinyl chloride powder, 316g of the crosslinking flexibilizer prepared in example 1, 380g of sodium carbonate and 8L of cyclohexanone into a reaction kettle at the same time, heating to 90 ℃, carrying out reflux reaction for 35 hours, carrying out rotary evaporation to recover a solvent, and washing and drying a solid obtained after the rotary evaporation by using water and acetone in sequence to obtain crosslinking modified polyvinyl chloride powder;
and secondly, adding 1kg of cross-linked modified polyvinyl chloride powder and 90g of calcium carbonate into an open mill simultaneously for melting and plastifying, then taking out the sheet, then preheating the sheet in a vulcanizer with the temperature of 170-180 ℃ for 10-15min, then pressurizing, exhausting, maintaining the pressure for 5-7min, and then shaping through a cold press to obtain the polyvinyl chloride sheet.
Comparative example 4:
the polyvinyl chloride sheet was prepared in the same manner as in example 2, except that the crosslinked toughener used in example 2 and prepared in example 1 was replaced with the crosslinked toughener prepared in comparative example 1.
Comparative example 5:
the polyvinyl chloride sheet was prepared in the same manner as in example 2, except that the crosslinking flexibilizer used in example 2 and prepared in example 1 was replaced with the crosslinking flexibilizer prepared in comparative example 1, and 221g of n-hexyltrimethoxysilane was added in the first step of the polyvinyl chloride sheet preparation process.
Comparative example 6:
the polyvinyl chloride sheet was prepared in the same manner as in example 2, except that the crosslinked toughener used in example 2, prepared in example 1, was replaced with the crosslinked toughener prepared in comparative example 2.
Comparative example 7:
the polyvinyl chloride sheet was prepared in the same manner as in example 2, except that the crosslinked toughener used in example 2, prepared in example 1, was replaced with the crosslinked toughener prepared in comparative example 3.
Test examples
(1) The polyvinyl chloride sheets prepared in example 2 and comparative examples 4 to 7 were cut into sheets of the same mass, and then placed in an oven at 260 ℃ for 1 hour, and then taken out to be cooled, and the mass of the sheets before and after the placement was measured as M0 and M1, respectively, and then the thermal decomposition mass loss rate P of the sheets in the high temperature oven was calculated as (M0-M1)/M0 × 100%, where P was 0.3% in example 2, 21.1% in comparative example 4, 4.6% in comparative example 5, 0.4% in comparative example 6, and 0.3% in comparative example 7, from which it was found that polyvinyl chloride had high thermal stability and hardly occurred thermal decomposition due to the direct introduction of a large amount of siloxane bonds into polyvinyl chloride in example 2, comparative example 6 and comparative example 7, and that n-hexyltrimethoxysilane was directly added in comparative example 5, through physical effect mixing, the n-hexyltrimethoxysilane is poor in compatibility with polyvinyl chloride, so that the n-hexyltrimethoxysilane is not uniformly dispersed in the polyvinyl chloride, and the heat-resistant stability of the polyvinyl chloride is reduced, and in the comparative example 4, the prepared polyvinyl chloride sheet is crosslinked into a net structure through the crosslinking flexibilizer containing the silicon-oxygen bond, so that a large number of silicon-oxygen bonds are contained in the net structure, and the heat stability of the polymer sheet is improved.
(2) The toughened polyvinyl chloride sheets prepared in example 2 and comparative examples 4 to 7 were tested for tensile properties in accordance with GB/T1040.3-2006, the sheet prepared in example 2 had a tensile strength of 22.36MPa, an elongation at break of 543.2%, the sheet prepared in comparative example 4 had a tensile strength of 22.28MPa, an elongation at break of 527.2%, the sheet prepared in comparative example 5 had a tensile strength of 22.31MPa, an elongation at break of 533.1%, the sheet prepared in comparative example 6 had a tensile strength of 22.34MPa, an elongation at break of 536.2%, the sheet prepared in comparative example 7 had a tensile strength of 18.95MPa, and an elongation at break of 482.7%, from which it was found that the sheet prepared in example 2 had high tensile strength and elongation at break, and that the distance between two polyvinyl chloride molecules was increased by the interval of the crosslinking toughening agent, so that the connected polyvinyl chloride molecules could not be bonded by intermolecular force, the crystallization degree of polyvinyl chloride molecules is reduced, the molecular chain of the crosslinking flexibilizer is connected through a large number of flexible groups of C-N bonds, C-Si bonds, C-O bonds and Si-O bonds, the toughness of the polyvinyl chloride molecules is improved, although the molecular distance is increased, the strength of two adjacent polyvinyl chloride molecules is not reduced but is increased because the two adjacent polyvinyl chloride molecules are connected through the crosslinking flexibilizer, the flexibility is reduced and the elongation at break is reduced because no siloxane bond is introduced in comparative example 4, meanwhile, N-hexyltrimethoxysilane is added in the comparative example 5 in a dyeing way, but the N-hexyltrimethoxysilane is not uniformly dispersed in the polyvinyl chloride and does not directly act on the molecular chain, so that the toughness is reduced relative to that of the example 2, and the toughness is reduced because the content of introduced ether bonds is reduced compared with that of the carbon-nitrogen bonds in the example 2 in the comparative example 6, meanwhile, in the comparative example 7, only one mercapto group is contained in the prepared toughening modifier, and the crosslinking into a net structure cannot be realized, so that the strength of the polymer is reduced, and meanwhile, polyvinyl chloride molecular chains are still bonded through intermolecular force although a certain interval exists through steric hindrance of the toughening modifier, so that the toughness of the polymer is greatly reduced.
(3) An aging test was conducted in accordance with GB/T18244-2000 "aging test method for waterproof building Material", in which the polyvinyl chloride sheets prepared in example 2 and comparative example 6 were placed in a xenon weather-resistant test chamber, and the irradiation intensity in the test chamber was controlled to 550W/m2After aging for 100 days at 100 ℃ and 60% humidity, the retention of elongation at break of the aged polyvinyl chloride sheet is determined according to the tensile properties of GB/T1040.3-2006, namely the elongation at break of the aged polyvinyl chloride sheet/the elongation at break of the polyvinyl chloride sheet before aging x 100%, the retention of elongation at break of example 2 is 99.3%, and the retention of elongation at break of comparative example 6 is 94.8%, so that it can be seen that, since the polyvinyl chloride does not introduce amino groups into the polymer in comparative example 6, although the polyvinyl chloride has the absorption of the ultraviolet light absorber and the siloxane bond to improve the thermal stability under the action of heat and light, the polyvinyl chloride still exists due to slight thermal decomposition, and a small amount of ultraviolet light can act on the polymer after absorption, and the polymer generates radicals under the action of light and heat, and the polymer is dehydrogenated under the induction of the radicals, while hydrogen chloride can accelerate the generation of free radicals and further accelerate the decomposition of the polymer, the generated hydrogen chloride can be directly absorbed by amino groups in the polymer in the embodiment 2 to blockThe catalytic action of hydrogen chloride on the decomposition of the polymer is achieved.
(III) example of Process for producing self-adhesive polyvinyl chloride Water-repellent coil
Example 3:
the surface of the polyvinyl chloride sheet prepared in example 2 was coated with a layer of epoxy resin adhesive, and a layer of aluminum foil layer was laminated on the surface of the polyvinyl chloride sheet by the adhesive and calendered by a calender to obtain a self-adhesive polyvinyl chloride waterproof roll, which was then directly peeled off to be adhered.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (7)
1. The self-adhesive polyvinyl chloride waterproof coiled material is characterized by comprising a polyvinyl chloride sheet and an aluminum foil layer, wherein the polyvinyl chloride sheet and the aluminum foil layer are bonded through an adhesive;
the preparation process of the polyvinyl chloride sheet comprises the following steps:
firstly, adding polyvinyl chloride powder, a crosslinking flexibilizer, sodium carbonate and cyclohexanone into a reaction kettle at the same time, heating to 80-90 ℃, performing reflux reaction for 35-38h, performing rotary evaporation to recover a solvent, and washing and drying a solid obtained after the rotary evaporation to obtain crosslinking modified polyvinyl chloride powder;
secondly, adding the crosslinked modified polyvinyl chloride powder and the calcium carbonate into an open mill simultaneously, performing melt plastication, discharging sheets, vulcanizing the sheets, and sizing by a cold press to obtain polyvinyl chloride sheets;
the preparation process of the crosslinking toughening agent is as follows:
step 1, weighing a certain amount of methyl 4-chloroacetoacetate, ethyl sorbate, ethanol and sodium ethoxide, simultaneously adding into a reaction kettle, heating to 70-100 ℃, carrying out reflux reaction for 3-4h, washing the product with deionized water for 4-5 times, drying and filtering with anhydrous sodium sulfate, and carrying out reduced pressure distillation on the filtrate to obtain acetyl unsaturated acid diethyl ester;
step 2: simultaneously adding acetyl unsaturated diethyl acetate and anhydrous acetone into a reaction kettle, simultaneously adding a platinum catalyst into the reaction kettle, continuously introducing nitrogen into the reaction kettle, simultaneously heating to 100-105 ℃, dropwise adding trimethoxy hydrosilane into the reaction kettle, controlling the reaction kettle to react for 3-4 hours at constant temperature after the dropwise adding is completed within 30min, then cooling to room temperature, removing the solvent and unreacted trimethoxy hydrosilane by rotary evaporation, repeatedly washing the product with water, and drying to obtain silanized acetyl unsaturated diethyl acetate;
and step 3: adding 2, 4-dihydroxybenzophenone into ethanol, stirring for dissolving, then adding solid caustic soda, heating to 75-80 ℃ after stirring for dissolving, then slowly dropwise adding silanized acetyl unsaturated acid diethyl ester into the reaction kettle, controlling the dropwise adding to be complete within 30min, carrying out constant-temperature reflux reaction for 6-7h after the dropwise adding is complete, and then carrying out filtering, washing and drying to obtain an intermediate product M1;
and 4, step 4: adding the intermediate product M1 and acetone into a reaction kettle, stirring and dissolving, dropwise adding sodium hydroxide to control the pH value of the solution to be 13, then adding 1, 3-diaminoguanidine hydrochloride into the reaction kettle, stirring and reacting at normal temperature for 3-4h, washing the product solution with deionized water, then layering to obtain an oil phase, drying the oil phase with anhydrous sodium sulfate, and then carrying out reduced pressure distillation to obtain an intermediate product M2;
and 5: mixing an intermediate product M2 and acetone according to a mass ratio of 1:1 to prepare a solution, then simultaneously adding 3-mercaptopropionic acid and thionyl chloride into a reaction vessel, heating to 60-65 ℃ for reflux reaction for 2-3h, then reducing to room temperature, adding the prepared intermediate product M2 solution and triethylamine, stirring for reaction for 4-5h, then performing rotary evaporation to remove the solvent and unreacted micromolecule substances, adding the evaporated product into water to wash away the generated salt, and obtaining the crosslinking flexibilizer.
2. The self-adhesive polyvinyl chloride waterproof roll as claimed in claim 1, wherein 328g of crosslinking toughening agent, 380g of sodium carbonate and 390g of cyclohexanone are added to each kilogram of PVC powder in the first step.
3. The self-adhesive polyvinyl chloride waterproof roll as claimed in claim 1, wherein 945-950g of ethyl sorbate, 4.6-4.7L of ethanol and 210-215g of sodium ethoxide are added per kg of methyl 4-chloroacetoacetate in step 1 of the preparation process of the crosslinking flexibilizer.
4. The self-adhesive polyvinyl chloride waterproof roll as claimed in claim 1, wherein in step 2 of the crosslinking flexibilizer preparation process, 440-446g of trimethoxyhydrosilane is added to each kilogram of the diethyl acetyl unsaturated acid, 10.6-11.2g of platinum catalyst is added, and 2.7-2.8L of anhydrous acetone is added.
5. The self-adhesive polyvinyl chloride waterproofing membrane according to claim 1, wherein 1.95-1.96kg of silanized diethyl acetyl unsaturated acid per kg of 2, 4-dihydroxybenzophenone in step 3 of the crosslinking flexibilizer preparation process is added, 620 g of solid caustic soda is added, and 3.2-3.3L of ethanol is added.
6. The self-adhesive polyvinyl chloride waterproofing membrane according to claim 1, wherein in step 4 of the crosslinking flexibilizer preparation process, 415g of 1, 3-diaminoguanidine hydrochloride is added per kg of intermediate M1.
7. The self-adhesive polyvinyl chloride waterproofing membrane according to claim 1, wherein in step 5 of the crosslinking flexibilizer preparation process, 140-145g of 3-mercaptopropionic acid, 180-186g of thionyl chloride and 400-410g of triethylamine were added to each kg of the intermediate M2.
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Inventor after: Nie Guanjun Inventor after: Zhang Xianshu Inventor after: Xu Lei Inventor before: Xu Lei |
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Effective date of registration: 20210218 Address after: 41007 east end of business center 101, Hunan environmental protection science and Technology Industrial Park, 199 Zhenhua Road, Yuhua District, Changsha City, Hunan Province Applicant after: HUNAN GUANYE WATERPROOF MATERIAL Co.,Ltd. Address before: 210012 unit 3, building 1, village 3, gongqingtuan Road, Yuhua street, Yuhuatai District, Nanjing City, Jiangsu Province Applicant before: Xu Lei |
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