CN114395069B - Plasticizer-free soft PVC (polyvinyl chloride) and preparation method thereof - Google Patents
Plasticizer-free soft PVC (polyvinyl chloride) and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000004800 polyvinyl chloride Substances 0.000 title description 86
- 229920000915 polyvinyl chloride Polymers 0.000 title description 85
- 239000004014 plasticizer Substances 0.000 claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 229920001577 copolymer Polymers 0.000 claims description 90
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 77
- 239000000178 monomer Substances 0.000 claims description 70
- 239000000725 suspension Substances 0.000 claims description 30
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 26
- 239000007795 chemical reaction product Substances 0.000 claims description 26
- 239000003999 initiator Substances 0.000 claims description 22
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000002270 dispersing agent Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- JCLFHZLOKITRCE-UHFFFAOYSA-N 4-pentoxyphenol Chemical compound CCCCCOC1=CC=C(O)C=C1 JCLFHZLOKITRCE-UHFFFAOYSA-N 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- 239000011261 inert gas Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 9
- 125000005842 heteroatom Chemical group 0.000 abstract description 4
- 125000003118 aryl group Chemical group 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract 1
- 239000005977 Ethylene Substances 0.000 abstract 1
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- 125000004434 sulfur atom Chemical group 0.000 abstract 1
- 239000000047 product Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 12
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 12
- 230000004048 modification Effects 0.000 description 11
- 238000012986 modification Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- 125000004437 phosphorous atom Chemical group 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- NXQMCAOPTPLPRL-UHFFFAOYSA-N 2-(2-benzoyloxyethoxy)ethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOCCOC(=O)C1=CC=CC=C1 NXQMCAOPTPLPRL-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920012485 Plasticized Polyvinyl chloride Polymers 0.000 description 1
- 229920000034 Plastomer Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000012660 binary copolymerization Methods 0.000 description 1
- 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 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—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
- C08F214/02—Monomers containing chlorine
- C08F214/04—Monomers containing two carbon atoms
- C08F214/06—Vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/02—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F228/00—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 bond to sulfur or by a heterocyclic ring containing sulfur
- C08F228/02—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 bond to sulfur or by a heterocyclic ring containing sulfur by a bond to sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F228/00—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 bond to sulfur or by a heterocyclic ring containing sulfur
- C08F228/06—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 bond to sulfur or by a heterocyclic ring containing sulfur by a heterocyclic ring containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
Abstract
The invention provides novel soft PVC without plasticizer, which is obtained by copolymerizing a first comonomer and VCM, wherein the first comonomer is ethylene containing heteroatom aromatic ring groups, and the heteroatom aromatic ring groups are provided with two alkyl molecular chains. The heteroatom is one of P, N, S atoms. According to the invention, a comonomer is introduced to prepare a copolymerization modified PVC material, and the mechanical property of the PVC material is still close to that of soft PVC modified by a conventional plasticizer even if no plasticizer is added. And the preparation method of the modified PVC is similar to that of the existing soft PVC, and the large-scale adjustment of a production line is not needed during industrial production.
Description
Technical Field
The invention belongs to the technical field of new materials, and particularly relates to soft PVC (polyvinyl chloride) without plasticizer and a preparation method thereof.
Background
Polyvinyl chloride (PVC), is a polymer obtained by polymerizing Vinyl Chloride Monomer (VCM) by a free radical polymerization mechanism under the action of an initiator or light and heat. PVC is one of the most common general-purpose plastics in the world to date and has very wide application. The product has wide application in building materials, industrial products, daily necessities, floor leathers, floor tiles, artificial leathers, pipes, wires and cables, packaging films, bottles, foaming materials, sealing materials, fibers and the like.
Depending on the application, PVC plastomers are often classified into: no plasticized PVC, plasticizer content 0; hard PVC, the plasticizer content is less than 10%; semi-hard PVC, the plasticizer content is 10-30%; soft PVC, the plasticizer content is 30-70%; the content of the plasticizer in the polyvinyl chloride paste plastic is more than 80%.
The plasticizer is added in the compounding process, generally does not react with the polymer chemically, and when the product is subjected to heat radiation or is contacted with an acid-base solution with strong extraction capacity, the product can be extracted or automatically migrates, and the physical and chemical properties of the product can be changed along with the change, so that the performance and the service life of the product are influenced. Also, since the plasticizer in PVC naturally overflows, a large amount of the plasticizer exudes particularly when heated. This has led to the strict prohibition on plasticizer-containing PVC, particularly soft PVC, for use in the fields of electronics, food packaging, consumer goods, and medical and health.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides soft PVC without plasticizer, which has the structural formula as follows:
wherein R is 1 Is one of P, N atoms, R 2 And R 3 The same/different; the R is 2 、R 3 Is C 3 -C 20 Of (a) an alkane.
Further, said R 2 And R 3 Same, are all C 6 -C 10 Linear alkanes of (1).
Further, the soft PVC without plasticizer has a structural formula as follows:
wherein R is 4 Is one of sulfonic acid group, phosphoric acid group or amino group, R 5 Is C 10 -C 15 Linear alkane of (2), R 6 Is C having a sulfonic or phosphoric group or an amino substituent 6 -C 8 Straight chain alkanes.
In addition, the invention also provides a preparation method of the soft PVC, which comprises the following steps:
s1, preparing a vinyl chloride monomer Amol and preparing a first copolymer monomer B mol; the first comonomer has the formula:
s2, adding the first copolymer monomer into deionized water, adding a dispersing agent, fully stirring and dispersing, adding an initiator, adjusting the temperature of the system to 40 +/-2 ℃, and maintaining for 3-5min to obtain a copolymer suspension.
S3, introducing inert gas to replace air in the reaction kettle, introducing vinyl chloride gas into the copolymer suspension, adjusting the temperature of the system to 50-70 ℃, and maintaining for 2-3 hours to obtain a reaction product.
And S4, carrying out solid-liquid separation, washing and drying on the reaction product to obtain the soft PVC.
Further, in step S1: the mole number B of the first copolymer monomer satisfies B = A/K 1 ，K 1 Taking 13-15 parts.
Further, R 1 Is one of P, N atoms, R 2 And R 3 The same/different; the R is 2 、R 3 Is C 3 -C 20 Of (a) an alkane.
Further, the step S3 of adjusting the system temperature to 50-70 ℃ and maintaining the system temperature for 2-3h comprises the following steps: firstly, adjusting the temperature of the system to 50-55 ℃, and maintaining for 60-65min; then adjusting the temperature of the system to 65-70 ℃, and maintaining the temperature until the reaction is finished.
Further, the step S1 also comprises the steps of preparing a second comonomer C mol; the structural formula of the second comonomer is:
Further, R 4 Is one of sulfonic acid group, phosphoric acid group or amino group, R 5 Is C 10 -C 15 Of linear alkanes of (a), R 6 Is C having a sulfonic or phosphoric group or an amino substituent 6 -C 8 Straight chain alkanes.
Further, step S2 further includes: firstly, adding a first copolymer monomer into deionized water, adding a dispersant, fully stirring and dispersing, and then adding an initiator; then adjusting the temperature of the system to 35 +/-2 ℃, maintaining for 3-5min, and adding a second comonomer; then adjusting the temperature of the system to 40 +/-2 ℃, and maintaining for 5-7min to obtain copolymer suspension.
The invention has at least one of the following advantages:
1. according to the invention, a comonomer is introduced to prepare a copolymerization modified PVC material, and the mechanical property of the PVC material is still close to that of soft PVC modified by a conventional plasticizer even if no plasticizer is added.
2. The preparation method of the modified PVC is similar to the preparation method of the existing soft PVC, and the large-scale adjustment of a production line is not needed during industrial production.
Drawings
FIG. 1 shows an infrared spectrum of pure PVC;
FIG. 2 shows an infrared spectrum of a binary copolymerization modified soft PVC according to the present invention;
FIG. 3 shows an IR spectrum of a terpolymer modified flexible PVC of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The definitions of the radicals and terms described in the specification and claims of the present application, including their definitions as examples, exemplary definitions, preferred definitions, definitions described in the tables, definitions of specific compounds in the examples, etc., may be combined with each other in any combination. The definitions of the groups and the structures of the compounds in such combinations and after the combination are within the scope of the present specification.
The term "C 3 -C 20 "is understood to mean having 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms," C 6 -C 10 "is understood to mean having 6, 7, 8, 9, 10 carbon atoms," C 10 -C 15 "is understood to mean having 10, 11, 12, 13, 14, 15 carbon atoms," C 6 -C 8 "is understood to mean having 6, 7, 8 carbon atoms.
The copolymer suspension of the invention contains a dispersant and an initiator, but the dispersant and the initiator can be added, and an auxiliary agent such as a terminator can be added according to the needs. The dispersant and the initiator selected by the invention are the dispersant and the initiator for the existing VMC suspension polymerization.
Example 1
A soft PVC without plasticizer is prepared by the following method:
s1, preparing a vinyl chloride monomer Amol and preparing a first copolymer monomer B mol; the first comonomer has the formula:
s2, adding the first copolymer monomer into deionized water, adding a dispersing agent, fully stirring and dispersing, adding an initiator, adjusting the temperature of the system to 40 +/-2 ℃, and maintaining for 4min to obtain a copolymer suspension.
S3, introducing inert gas to replace air in the reaction kettle, introducing vinyl chloride gas into the copolymer suspension, adjusting the temperature of the system to 60 ℃, and maintaining for 2.5 hours to obtain a reaction product.
And S4, carrying out solid-liquid separation, washing and drying on the reaction product to obtain the soft PVC.
Wherein: the mole number B of the first copolymer monomer satisfies B = A/K 1 ，K 1 And taking 14.R is 1 Is a N atom, R 2 And R 3 The same; the R is 2 、R 3 Are all C 12 Of (a) an alkane.
The structural formula of the product is as follows:
Example 3
A soft PVC without plasticizer is prepared by the following method:
s1, preparing a vinyl chloride monomer Amol and preparing a first copolymer monomer B mol; the first comonomer has the formula:
s2, adding the first copolymer monomer into deionized water, adding a dispersing agent, fully stirring and dispersing, adding an initiator, adjusting the temperature of the system to 40 +/-2 ℃, and maintaining for 3min to obtain a copolymer suspension.
S3, introducing inert gas to replace air in the reaction kettle, introducing vinyl chloride gas into the copolymer suspension, adjusting the system temperature to 50 ℃, and maintaining for 3 hours to obtain a reaction product.
And S4, carrying out solid-liquid separation, washing and drying on the reaction product to obtain the soft PVC.
Wherein: the mole number B of the first copolymer monomer satisfies B = A/K 1 ，K 1 And taking 13.R 1 Is a P atom, R 2 And R 3 The same; the R is 2 、R 3 Are all C 3 Of (a) an alkane.
The structural formula of the product is as follows:
Example 4
A soft PVC without plasticizer is prepared by the following method:
s1, preparingPreparing a first copolymer monomer B mol by using a vinyl chloride monomer Amol; the first comonomer has the formula:
s2, adding the first copolymer monomer into deionized water, adding a dispersing agent, fully stirring and dispersing, adding an initiator, adjusting the temperature of the system to 40 +/-2 ℃, and maintaining for 4min to obtain a copolymer suspension.
S3, introducing inert gas to replace air in the reaction kettle, introducing vinyl chloride gas into the copolymer suspension, adjusting the temperature of the system to 60 ℃, and maintaining for 2.5 hours to obtain a reaction product.
And S4, carrying out solid-liquid separation, washing and drying on the reaction product to obtain the soft PVC.
Wherein: the mole number B of the first copolymer monomer satisfies B = A/K 1 ，K 1 And taking 14.R is 1 Is a N atom, R 2 And R 3 Different; the R is 2 Is C 10 Alkane of (A), R 3 Is C 16 Of (a) an alkane.
The structural formula of the product is:
Example 5
A soft PVC without plasticizer is prepared by the following method:
s1, preparing a vinyl chloride monomer Amol, a first comonomer B mol and a second comonomer C mol. The first comonomer has the formula:
the structural formula of the second comonomer is:
s2, adding the first copolymer monomer and the second copolymer monomer into deionized water, adding an initiator after full dispersion, adjusting the temperature of the system to 40 +/-2 ℃, and maintaining for 5min to obtain a copolymer suspension.
S3, introducing inert gas to replace air in the reaction kettle, introducing vinyl chloride gas into the copolymer suspension, adjusting the system temperature to 70 ℃, and maintaining for 2 hours to obtain a reaction product.
And S4, carrying out solid-liquid separation, washing and drying on the reaction product to obtain the soft PVC.
The mole number B of the first copolymer monomer satisfies B = A/K 1 ，K 1 And taking 14.R 1 Is a N atom, R 2 And R 3 Different; the R is 2 Is C 10 Alkane of (A), R 3 Is C 16 Of (a) an alkane. The mole number C of the second copolymer monomer satisfies C = A/K 2 ，K 2 And taking 27.
Wherein R is 1 Is a N atom, R 2 And R 3 Different; the R is 2 Is C 10 Alkane of (A), R 3 Is C 16 Of (a) an alkane. R 4 Is amino, R 5 Is C 10 -C 15 Of linear alkanes of (a), R 6 Is C having an amino substituent 6 -C 8 Straight chain alkanes.
The structural formula of the prepared product is as follows:
wherein R is 1 Is a N atom, R 2 And R 3 Different; the R is 2 Is C 10 Alkane of R 3 Is C 16 Of (a) an alkane. R 4 Is amino, R 5 Is C 10 -C 15 Linear alkane of (2), R 6 Is C having an amino substituent 6 -C 8 Straight chain alkanes.
Example 7
A soft PVC without plasticizer is prepared by the following method:
s1, preparing a vinyl chloride monomer Amol, a first comonomer B mol and a second comonomer C mol. The first comonomer has the structural formula:
the structural formula of the second comonomer is:
s2, adding the first copolymer monomer and the second copolymer monomer into deionized water, adding an initiator after full dispersion, adjusting the temperature of the system to 40 +/-2 ℃, and maintaining for 4min to obtain a copolymer suspension.
S3, introducing inert gas to replace air in the reaction kettle, introducing vinyl chloride gas into the copolymer suspension, adjusting the temperature of the system to 60 ℃, and maintaining for 2.5 hours to obtain a reaction product.
And S4, carrying out solid-liquid separation, washing and drying on the reaction product to obtain the soft PVC.
The mole number B of the first copolymer monomer satisfies B = A/K 1 ，K 1 And taking 14.R 1 Is a P atom, R 2 And R 3 Different; the R is 2 Is C 10 Alkane of R 3 Is C 16 Of (a) an alkane. The mole number C of the second copolymer monomer satisfies C = A/K 2 ，K 2 And taking 25.
Wherein R is 1 Is a P atom, R 2 And R 3 Different; the R is 2 Is C 10 Alkane of (A), R 3 Is C 16 Of (a) an alkane. R 4 Is a phosphate group, R 5 Is C 10 -C 15 Linear alkane of (2), R 6 Is C having a substituent of a phosphate group 6 -C 8 Straight chain alkanes.
The structural formula of the prepared product is as follows:
wherein R is 1 Is a P atom, R 2 And R 3 Different; said R is 2 Is C 10 Alkane of (A), R 3 Is C 16 Of (a) an alkane. R 4 Is a phosphate group, R 5 Is C 10 -C 15 Linear alkane of (2), R 6 Is C having a substituent of a phosphate group 6 -C 8 Straight chain alkanes.
Example 8
A soft PVC without plasticizer is prepared by the following method:
s1, preparing a vinyl chloride monomer Amol, a first comonomer B mol and a second comonomer C mol. The first comonomer has the formula:
the structural formula of the second comonomer is:
s2, adding the first copolymer monomer and the second copolymer monomer into deionized water, adding an initiator after full dispersion, adjusting the temperature of the system to 40 +/-2 ℃, and maintaining for 4min to obtain a copolymer suspension.
S3, introducing inert gas to replace air in the reaction kettle, introducing vinyl chloride gas into the copolymer suspension, adjusting the temperature of the system to 60 ℃, and maintaining for 2.5 hours to obtain a reaction product.
And S4, carrying out solid-liquid separation, washing and drying on the reaction product to obtain the soft PVC.
The mole number B of the first copolymer monomer satisfies B = A/K 1 ，K 1 And taking 14.R 1 Is a N atom, R 2 And R 3 Different; the R is 2 Is C 10 Alkane of (A), R 3 Is C 16 Of (a) an alkane. The mole number C of the second copolymer monomer satisfies C = A/K 2 ，K 2 And taking 27.
Wherein R is 1 Is a N atom, R 2 And R 3 Different; the R is 2 Is C 10 Alkane of (A), R 3 Is C 16 Of an alkane. R 4 Is a sulfonic acid group, R 5 Is C 10 -C 15 Linear alkane of (2), R 6 Is C having a substituent of a phosphate group 6 -C 8 Straight chain alkanes.
The structural formula of the prepared product is as follows:
wherein R is 1 Is a N atom, R 2 And R 3 Different; the R is 2 Is C 10 Alkane of (A), R 3 Is C 16 Of (a) an alkane. R 4 Is a sulfonic acid group, R 5 Is C 10 -C 15 Of linear alkanes of (a), R 6 Is C having a substituent of a phosphate group 6 -C 8 Straight chain alkanes.
Example 9
A soft PVC without plasticizer is prepared by the following method:
s1, preparing a vinyl chloride monomer Amol, a first comonomer B mol and a second comonomer C mol. The first comonomer has the structural formula:
the structural formula of the second comonomer is:
s2, adding the first copolymer monomer and the second copolymer monomer into deionized water, adding an initiator after full dispersion, adjusting the temperature of the system to 40 +/-2 ℃, and maintaining for 4min to obtain a copolymer suspension.
S3, introducing inert gas to replace air in the reaction kettle, introducing vinyl chloride gas into the copolymer suspension, adjusting the temperature of the system to 60 ℃, and maintaining for 2.5 hours to obtain a reaction product.
And S4, carrying out solid-liquid separation, washing and drying on the reaction product to obtain the soft PVC.
The mole number B of the first copolymer monomer satisfies B = A/K 1 ，K 1 And taking 14.R 1 Is a N atom, R 2 And R 3 Different; the R is 2 Is C 10 Alkane of (A), R 3 Is C 16 Of (a) an alkane. The mole number C of the second copolymer monomer satisfies C = A/K 2 ，K 2 And taking 27.
Wherein R is 1 Is a N atom, R 2 And R 3 Different; the R is 2 Is C 10 Alkane of (A), R 3 Is C 16 Of (a) an alkane. R 4 Is amino, R 5 Is C 10 -C 15 Linear alkane of (2), R 6 Is C having a substituent of a phosphate group 6 -C 8 Straight chain alkanes.
The structural formula of the prepared product is as follows:
wherein R is 1 Is a N atom, R 2 And R 3 Different; the R is 2 Is C 10 Alkane of (A), R 3 Is C 16 Of (a) an alkane. R is 4 Is amino, R 5 Is C 10 -C 15 Linear alkane of (2), R 6 Is C having a substituent of a phosphate group 6 -C 8 A straight chain alkane.
Example 10
A soft PVC without plasticizer is prepared by the following method:
s1, preparing a vinyl chloride monomer Amol, a first comonomer B mol and a second comonomer C mol. The first comonomer has the structural formula:
the structural formula of the second comonomer is:
s2, adding the first copolymer monomer and the second copolymer monomer into deionized water, adding an initiator after full dispersion, adjusting the temperature of the system to 40 +/-2 ℃, and maintaining for 4min to obtain a copolymer suspension.
S3, introducing inert gas to replace air in the reaction kettle, introducing vinyl chloride gas into the copolymer suspension, adjusting the temperature of the system to 60 ℃, and maintaining for 2.5 hours to obtain a reaction product.
And S4, carrying out solid-liquid separation, washing and drying on the reaction product to obtain the soft PVC.
The mole number B of the first copolymer monomer satisfies B = A/K 1 ，K 1 And taking 14.R is 1 Is a N atom, R 2 And R 3 Different; the R is 2 Is C 10 Alkane of (A), R 3 Is C 16 Of an alkane. The mole number C of the second copolymer monomer satisfies C = A/K 2 ，K 2 And taking 27.
Wherein R is 1 Is a N atom, R 2 And R 3 Different; the R is 2 Is C 10 Alkane of (A), R 3 Is C 16 Of (a) an alkane. R 4 Is a phosphate group, R 5 Is C 10 -C 15 Linear alkane of (2), R 6 Is C having an amino substituent 6 -C 8 Straight chain alkanes.
The structural formula of the prepared product is as follows:
wherein R is 1 Is a N atom, R 2 And R 3 Different; the R is 2 Is C 10 Alkane of R 3 Is C 16 Of (a) an alkane. R 4 Is a phosphate group, R 5 Is C 10 -C 15 Of linear alkanes of (a), R 6 Is C having an amino substituent 6 -C 8 Straight chain alkanes.
Example 11
Plasticizer-free soft PVC based on examples 1-10, wherein: s3, adjusting the system temperature to 50-70 ℃, and maintaining for 2-3h, wherein the method comprises the following steps: firstly, adjusting the temperature of the system to 50-55 ℃, and maintaining for 60-65min; then adjusting the temperature of the system to 65-70 ℃, and maintaining the temperature until the reaction is finished.
Taking the embodiment 10 as an example, the step S3 of the embodiment 10 includes: regulating the temperature of the system to 60 ℃, and maintaining for 2.5h to obtain a reaction product. Instead, the procedure of example 11 was used: firstly, adjusting the temperature of the system to 53 ℃, and maintaining for 60min; then adjusting the temperature of the system to 65 ℃, and maintaining for 40min to obtain a reaction product. It can be seen that under the same conditions, the overall time for copolymerization can be significantly reduced by using the stepwise temperature control method described in example 11.
Example 12
Plasticizer-free soft PVC based on examples 5-10, wherein: step S2 further includes: firstly, adding a first copolymer monomer into deionized water, adding a dispersant, fully stirring and dispersing, and then adding an initiator; then adjusting the temperature of the system to 35 +/-2 ℃, maintaining for 3-5min, and adding a second comonomer; then adjusting the temperature of the system to 40 +/-2 ℃, and maintaining for 5-7min to obtain copolymer suspension.
Taking the embodiment 10 as an example, the step S2 of the embodiment 10 includes: adding a first copolymer monomer and a second copolymer monomer into deionized water, adding an initiator after full dispersion, adjusting the temperature of the system to 40 +/-2 ℃, and maintaining for 4min to obtain a copolymer suspension. Instead, the method of example 12 was used: firstly, adding a first copolymer monomer into deionized water, adding a dispersant, fully stirring and dispersing, and then adding an initiator; then adjusting the temperature of the system to 35 +/-2 ℃, and adding a second comonomer after maintaining for 4 min; then adjusting the temperature of the system to 40 +/-2 ℃ and maintaining for 6min to obtain a copolymer suspension. Although the total time of the constant temperature in step S2 was increased from 4min to 10min, the elongation at break of the copolymerization product of example 12 was increased from 291.12% in example 10 to 302.19% in example 12, compared to the copolymerization product of example 10. It can be seen that the final mechanical properties of the copolymerization product can be improved to a certain extent by using the temperature control method of example 12, which is specifically indicated that the elongation at break is improved on the basis that the tensile strength is not significantly changed.
Comparative example 1
And adding 50 parts of dioctyl phthalate into 100 parts of PVC for modification to obtain soft PVC.
Comparative example 2
And adding 50 parts of diethylene glycol dibenzoate into 100 parts of PVC for modification to obtain the soft PVC.
Comparative example 3
A soft PVC without plasticizer is prepared by the following method:
s1, preparing a vinyl chloride monomer Amol and a second comonomer C mol. The structural formula of the second comonomer is:
s2, adding the first copolymer monomer into deionized water, adding a dispersing agent, fully stirring and dispersing, adding an initiator, adjusting the temperature of the system to 40 +/-2 ℃, and maintaining for 4min to obtain a copolymer suspension.
S3, introducing inert gas to replace air in the reaction kettle, introducing vinyl chloride gas into the copolymer suspension, adjusting the temperature of the system to 60 ℃, and maintaining for 2.5 hours to obtain a reaction product.
And S4, carrying out solid-liquid separation, washing and drying on the reaction product to obtain the soft PVC.
The mole number C of the second copolymer monomer satisfies C = A/K 2 ，K 2 And taking 27.
Wherein R is 4 Is a phosphate group, R 5 Is C 10 -C 15 Linear alkane of (2), R 6 Is C having an amino substituent 6 -C 8 Straight chain alkanes.
The structural formula of the prepared product is as follows:
wherein R is 4 Is a phosphate group, R 5 Is C 10 -C 15 Linear alkane of (2), R 6 Is C having an amino substituent 6 -C 8 A straight chain alkane.
Comparative example 4
The preparation of example 1 was carried out, wherein the molar number B of the first copolymer monomers satisfies B = A/K 1 ，K 1 And 10 is taken.
Comparative example 5
The preparation of example 1 was used, wherein the number of moles B of the first copolymer monomer satisfied B = A/K 1 ，K 1 And 18 are taken.
Comparative example 6
The preparation method of example 5 was employed, wherein the mole number C of the second copolymer monomer satisfied C = a/K 2 ，K 2 And taking 30.
Comparative example 7
The preparation method of example 5 was employed, wherein the mole number C of the second copolymer monomer satisfied C = a/K 2 ，K 2 And taking 23.
Comparative example 8
The preparation was carried out as described in example 1, wherein R of the first copolymer monomer 1 Is a C atom.
The test method comprises the following steps:
1. and (3) testing mechanical properties: the tensile properties of the soft PVC were determined according to GB/T1040.1-2006 "Plastic tensile test methods". And (3) testing temperature: 25 ℃; stretching rate: 50mm/min. Three tests were averaged to an accuracy of 0.01.
2. And (3) hardness testing: and (3) manufacturing sample strips according to the GB/T531-2008 standard, testing, selecting 3 points of each group of samples, testing for 1 time at each point, and taking a median.
3. Oil extraction resistance: the soft PVC material 30 x 45 x 3mm was placed in ethanol solvent and soaked in a closed environment at 60 ℃ for 5 hours. And after soaking, drying and weighing, and calculating the mass loss percentage of the soft PVC material to evaluate the extraction performance of the soft PVC material. Three tests were averaged to an accuracy of 0.01.
4. The red spectral measurements were performed on pure PVC, example 1 and example 8.
The results of the tests 1-3 are shown in the following table:
TABLE 1 test results of mechanical properties, hardness, and resistance to oil extraction
FIG. 1 shows the IR spectrum of a pure PVC standard, and FIG. 2 shows the IR spectrum of a flexible PVC obtained in example 1 of the present invention. As can be seen from FIG. 2, the PVC modified with the first comonomer is in the range of 1550-1620cm -1 A relatively obvious pyridine characteristic absorption peak appears, and the modified PVC contains a first comonomer. FIG. 3 is a chart showing an infrared spectrum of a flexible PVC obtained in example 8 of the present invention. As can be seen from FIG. 3, the PVC modified by the first comonomer and the second comonomer is in the range of 1550-1620cm -1 A relatively remarkable pyridine characteristic absorption peak appears at 1100cm -1 A relatively obvious sulfonic acid group characteristic absorption peak appears nearby, and is 1050cm -1 Phosphate characteristic absorption peaks appear nearby, and it can be seen that the modified PVC contains a first comonomer and a second comonomer.
As shown in Table 1, the hardness and mechanical properties of the PVC modified by copolymerization according to the invention are compared with those of PVC modified by adding plasticizer, so that the PVC modified by copolymerization according to the invention with the specific formula amount of the first comonomer can be preparedA soft PVC plasticized and modified without a plasticizer was obtained, and the result was equivalent to a soft PVC containing 50% by mass of a plasticizer. As can be seen from comparative examples 4 and 5, the elongation at break of the copolymer is markedly reduced by adding the first comonomer in excess or in deficiency. Therefore, in the copolymerization reaction of the present invention, B = a/K is satisfied only in the number B of moles of the first copolymer monomer 1 ，K 1 When 13-15 parts are taken, the PVC can play a role of plasticizing and modifying the PVC.
As can be seen from Table 1, the mechanical properties of PVC can be significantly improved by using the comonomer of the invention to carry out copolymerization modification on PVC, and the specific expression is as follows: after the first comonomer is adopted for copolymerization modification, the elongation at break of the modified PVC is slightly lower than that of PVC modified by 50% of plasticizer, but the tensile strength is improved. After the first comonomer and the second comonomer are adopted for copolymerization modification, the breaking elongation of the modified PVC is equivalent to that of PVC modified by 50% of plasticizer, and the tensile strength is not different from that of the PVC modified by the first comonomer alone. However, as can be seen from comparative example 3, the tensile strength of the modified PVC is not changed much after the second comonomer is added alone for copolymerization modification, but the elongation at break is slightly better than that of the conventional rigid PVC, but the modification effect is not obvious. It can be seen that the second comonomer alone is not effective in improving the plasticity of PVC when used. Therefore, when the second comonomer is used together with the first comonomer, the performance of the modified PVC is improved, and the plastic modification effect of the first comonomer on the PVC is further improved mainly due to the synergistic effect of the second comonomer on the first comonomer.
However, it is understood from comparative examples 6 and 7 that when the second comonomer is added in excess or in deficiency, the elongation at break of the copolymer is significantly reduced as compared to example 5. However, the elongation at break of the copolymer was improved to some extent compared to example 1. Therefore, in the copolymerization reaction of the present invention, C = a/K is satisfied only at the mole number C of the second copolymer monomer 2 ，K 2 When 25 to 28 is used, a good synergistic effect on the first comonomer can be achieved.
Furthermore, from comparative example 8, R of the first copolymer monomer 1 Selecting P,When one of N atoms is used, the PVC can be subjected to good plasticizing modification. But when R is 1 When the C atom is used, namely, when the heteroatom aromatic ring is changed into a benzene ring, the plasticizing modification effect of the first copolymer monomer on PVC is obviously reduced and is only slightly stronger than that of unmodified PVC.
It is to be noted and understood that various modifications and improvements can be made to the invention described in detail above without departing from the spirit and scope of the invention as claimed. Accordingly, the scope of the claimed subject matter is not limited by any of the specific exemplary teachings provided.
Claims (7)
1. A soft PVC without plasticizer, characterized in that it has the structural formula:
wherein R is 1 Is one of P, N atoms, R 2 And R 3 The same/different; the R is 2 、R 3 Is C 3 -C 20 An alkane of (a);
the soft PVC without the plasticizer is prepared by the following method:
s1, preparing a vinyl chloride monomer Amol and preparing a first copolymer monomer B mol; the first comonomer has the structural formula:
wherein R is 1 Is one of P, N atoms, R 2 And R 3 The same/different; the R is 2 、R 3 Is C 3 -C 20 The alkane of (1); the mole number B of the first copolymer monomer satisfies B = A/K 1 ，K 1 Taking 13 to 15
S2, adding a first copolymer monomer into deionized water, adding a dispersing agent, fully stirring and dispersing, adding an initiator, adjusting the temperature of the system to 40 +/-2 ℃, and maintaining for 3-5min to obtain a copolymer suspension;
s3, introducing inert gas to replace air in the reaction kettle, introducing vinyl chloride gas into the copolymer suspension, adjusting the temperature of the system to 50-70 ℃, and maintaining for 2-3 hours to obtain a reaction product;
and S4, carrying out solid-liquid separation, washing and drying on the reaction product to obtain the soft PVC.
2. The plasticizer-free soft PVC of claim 1, wherein R is 2 And R 3 Same are all C 6 -C 10 Linear alkanes of (1).
3. The plasticizer-free soft PVC of claim 1, wherein the plasticizer-free soft PVC has the formula:
wherein R is 4 Is one of sulfonic acid group, phosphoric acid group or amino group, R 5 Is C 10 -C 15 Linear alkane of (2), R 6 Is C having a sulfonic acid group or a phosphoric acid group or an amino substituent 6 -C 8 Straight chain alkanes.
4. The preparation method of the soft PVC is characterized by comprising the following steps:
s1, preparing a vinyl chloride monomer Amol and preparing a first copolymer monomer B mol; the first comonomer has the structural formula:
s2, adding a first copolymer monomer into deionized water, adding a dispersing agent, fully stirring and dispersing, adding an initiator, adjusting the temperature of the system to 40 +/-2 ℃, and maintaining for 3-5min to obtain a copolymer suspension;
s3, introducing inert gas to replace air in the reaction kettle, introducing vinyl chloride gas into the copolymer suspension, adjusting the temperature of the system to 50-70 ℃, and maintaining for 2-3 hours to obtain a reaction product;
s4, carrying out solid-liquid separation, washing and drying on the reaction product to obtain the soft PVC;
R 1 is one of P, N atoms, R 2 And R 3 The same/different; the R is 2 、R 3 Is C 3 -C 20 An alkane of (a);
in step S1: the mole number B of the first copolymer monomer satisfies B = A/K 1 ，K 1 Taking 13-15 parts.
5. The process for preparing flexible PVC according to claim 4, wherein in step S3, the temperature of the system is adjusted to 50-70 ℃ and maintained for 2-3h by the following steps: firstly, adjusting the temperature of the system to 50-55 ℃, and maintaining for 60-65min; then adjusting the temperature of the system to 65-70 ℃, and maintaining the temperature until the reaction is finished.
6. Process for the preparation of flexible PVC according to claim 4, wherein step S1 further comprises the preparation of a second comonomer C mol; the second comonomer has the structural formula:
R 4 is one of sulfonic acid group, phosphoric acid group or amino group, R 5 Is C 10 -C 15 Linear alkane of (2), R 6 Is C having a sulfonic or phosphoric group or an amino substituent 6 -C 8 A straight chain alkane.
7. The process for the preparation of flexible PVC according to claim 6, wherein step S2 further comprises: firstly, adding a first copolymer monomer into deionized water, fully dispersing, and then adding an initiator; then adjusting the temperature of the system to 35 +/-2 ℃, maintaining for 3-5min, and adding a second comonomer; then adjusting the temperature of the system to 40 +/-2 ℃, and maintaining for 5-7min to obtain copolymer suspension.
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Denomination of invention: A flexible PVC without plasticizers and its preparation method Granted publication date: 20230321 Pledgee: Kunming Branch of China Minsheng Bank Co.,Ltd. Pledgor: YUNNAN ZHENGBANG TECHNOLOGY CO.,LTD. Registration number: Y2023530000069 |