CN114230777A - Soft polyvinyl chloride and star-shaped block macromolecule green plasticizer for soft polyvinyl chloride - Google Patents
Soft polyvinyl chloride and star-shaped block macromolecule green plasticizer for soft polyvinyl chloride Download PDFInfo
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- CN114230777A CN114230777A CN202210029206.1A CN202210029206A CN114230777A CN 114230777 A CN114230777 A CN 114230777A CN 202210029206 A CN202210029206 A CN 202210029206A CN 114230777 A CN114230777 A CN 114230777A
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- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 63
- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 63
- 239000004014 plasticizer Substances 0.000 title claims abstract description 55
- 229920002521 macromolecule Polymers 0.000 title claims abstract description 31
- 239000004626 polylactic acid Substances 0.000 claims abstract description 63
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 48
- 230000009477 glass transition Effects 0.000 claims abstract description 10
- 125000000524 functional group Chemical group 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 13
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 claims description 9
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- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
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- 229920001434 poly(D-lactide) Polymers 0.000 claims description 6
- 229920001244 Poly(D,L-lactide) Polymers 0.000 claims description 3
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- 238000013508 migration Methods 0.000 abstract description 4
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- 238000001291 vacuum drying Methods 0.000 description 8
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- 238000002360 preparation method Methods 0.000 description 7
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- 238000006243 chemical reaction Methods 0.000 description 6
- 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 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 4
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 3
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
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- 230000037230 mobility Effects 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 108010039918 Polylysine Proteins 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 125000004185 ester group Chemical group 0.000 description 1
- GPQWKLDEDGOJQH-UHFFFAOYSA-N ethane-1,1,1,2-tetramine Chemical compound NCC(N)(N)N GPQWKLDEDGOJQH-UHFFFAOYSA-N 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 210000002216 heart Anatomy 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229920006150 hyperbranched polyester Polymers 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
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- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920000962 poly(amidoamine) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000656 polylysine Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
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- 150000003141 primary amines Chemical class 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
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- 150000003335 secondary amines Chemical group 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
- C08G63/6852—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from hydroxy carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
Abstract
The invention discloses soft polyvinyl chloride and a star-shaped block macromolecule green plasticizer for the soft polyvinyl chloride, which is provided with an inner core with at least three functional groups and at least three block macromolecule arms consisting of Polycaprolactone (PCL) with good biocompatibility and degradability and polylactic acid (PLA), wherein a PLA hard block with higher glass transition temperature is distributed inside and is directly connected with the inner core, and a PCL soft block with lower glass transition temperature is distributed outside the star-shaped macromolecule. The macromolecular green plasticizer can be uniformly mixed with PVC according to different proportions. Compared with commercial PVC products plasticized by diisooctyl phthalate, the PVC products plasticized by the macromolecular green plasticizer have higher toughness under the condition of keeping excellent elongation at break, and the plasticizer has higher migration resistance, so that the PVC products are safer and more environment-friendly and are more suitable for being applied in the field of biomedicine.
Description
Technical Field
The invention relates to the field of resin plasticization, in particular to soft polyvinyl chloride and a star-shaped block macromolecule green plasticizer for the soft polyvinyl chloride.
Background
PVC is a widely used thermoplastic polymer with a yield inferior to polyethylene and polypropylene in the world plastic market due to its excellent physical properties, good chemical resistance and low cost. Since PVC itself is brittle and has poor stability to light and heat, a large amount of plasticizer is incorporated into PVC in order to improve its processability. The addition of the plasticizer improves the extrudability of PVC, reduces melt viscosity, reduces elastic modulus, and provides durability and flexibility that facilitates the use of PVC in a variety of fields such as food packaging, toys, flooring, wallpaper, tubing, hoses, cables, and medical devices.
At present, the most common plasticizer in the market is phthalate, which accounts for more than 80% of the whole plasticizer industry. Due to the low cost and good mechanical properties, di (2-ethylhexyl) phthalate (DEHP) is used in an amount of about 60% of phthalate plasticizers. However, many studies have shown that phthalate plasticizers tend to migrate from PVC substrates to other media in contact therewith, and that migrating phthalate plasticizers can act as endocrine disrupters, poisoning the liver, heart, kidneys, lungs, testes and other organs. Since the 40's of the 20 th century, there has been much controversy in its application in the biomedical field.
Among the numerous environmentally friendly green plasticizers that do not contain phthalates, macromolecular plasticizers are generally preferred over small molecule analogs due to their lower mobility. In addition, the multi-point synergistic effect between PVC and the macromolecular plasticizer can overcome the leaching problem and keep the long-term mechanical property stable. Polycaprolactone (PCL), which has excellent biocompatibility and degradability, is one of the most attractive varieties of PVC "green" plasticizers. In the field of macromolecules, rational design of the topology of macromolecular materials is very important to achieve their optimal performance. In this respect, PCL plasticizers of branched structure are more effective in improving the flowability of PVC systems than PCL plasticizers of linear structure because of their high number of chain end groups, high free volume and flowability. For example, Kwak et al report that a highly branched copolymer obtained by one-pot copolymerization of Cyclohexadenlactone (CL) and glycidol in ACS Sustainable chem. Eng. journal of 2018, volume 6, 9006-page 9017 can provide PVC (plasticizer to PVC mass ratio of 60%) with high ductility (310-390%) and good tensile strength (12-16 MPa). Kwak et al reported that star PCL initiated by dipentaerythritol can significantly improve ductility of PVC systems (up to 380%) in ACS appl.Mater.Interfaces journal 2014, volume 6, page 11118-. Currently, although there are many reports on obtaining high ductility PVC elastomers by PCL-based plasticizers, their high ductility (about 350%) is always obtained at the expense of a significant reduction in tensile strength (typically less than 50% of the original tensile strength). Therefore, it remains a great challenge how to make PVC systems with better ductility, less loss of tensile strength, and thus higher toughness.
Disclosure of Invention
The invention aims to solve the technical problem of providing soft polyvinyl chloride and a star-shaped block macromolecule green plasticizer for the soft polyvinyl chloride, overcoming the defects of the existing PVC plasticizing system, wherein the plasticizer can be well and uniformly mixed with PVC according to different proportions, so that the plasticized PVC has excellent ductility and high elongation at break. The product after PVC plasticization has excellent ductility, and has higher toughness and higher migration resistance compared with the commercial DEHP plasticized PVC product, thereby being safer and more environment-friendly and being more suitable for application in the biomedical field.
In order to solve the technical problems, the invention adopts the technical scheme that: a star block macromolecule green plasticizer for soft polyvinyl chloride is represented by formula (I):
the structure of the star-shaped block macromolecular green plasticizer (I) is composed of three parts: the first is an inner core connected with a star-shaped macromolecular arm through a multifunctional group; the polylactic acid PLA block inner arm is directly connected with the inner core; and the third is the outer arm of the PCL block of the polycyclocaprolactone connected with the PLA block.
The inner core at least contains three functional group atoms X connected with PLA, wherein X is oxygen or nitrogen, the number of X is t +2, and t is an integer more than or equal to 1.
The inner arm is a PLA hard block with high glass transition temperature, the polymerization degree of the PLA hard block is m, and m is 10-40; the outer arm is a PCL soft block with low glass transition temperature, the polymerization degree of the PCL soft block is n, and n is 10-160.
Preferably, m is 20 to 30, and n is 40 to 60.
The PLA blocks are mixed PLA, levorotatory PLA and dextrorotatory PLA, wherein the mixed PLA is represented by PDLLA, the levorotatory PLA is represented by PLLA, and the dextrorotatory PLA is represented by PDLA.
Preferably, the PLA blocks are PLLA and PDLA. More preferably, the PLA block is PLLA.
A flexible polyvinyl chloride comprising:
(A) polyvinyl chloride, and
(B) the star-shaped block macromolecule green plasticizer.
The polyvinyl chloride resin composition comprises 40-80 parts by weight of star-shaped block macromolecule green plasticizer, preferably 40-60 parts by weight per 100 parts by weight of polyvinyl chloride.
The invention has the beneficial effects that: the plasticizer is suitable for an inner core with at least three functional groups, and at least three block macromolecule arms consisting of good biocompatibility and degradable Polycyclocaprolactone (PCL) and polylactic acid (PLA), wherein the PLA hard block with higher glass transition temperature is distributed inside and is directly connected with the inner core, and the PCL soft block with lower glass transition temperature is distributed outside the star-shaped macromolecule. The macromolecular green plasticizer can be uniformly mixed with PVC according to different proportions. Compared with commercial PVC products plasticized by diisooctyl phthalate, the PVC products plasticized by the macromolecular green plasticizer have higher toughness under the condition of keeping excellent elongation at break, and the plasticizer has higher migration resistance, so that the PVC products are safer and more environment-friendly and are more suitable for being applied in the field of biomedicine.
Drawings
FIG. 1 shows a star block macromolecular plasticizer of the invention1H NMR spectrum.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments obtained by a person skilled in the art without making any inventive step are within the scope of the present invention.
The star-shaped block macromolecule green plasticizer for the soft polyvinyl chloride is shown by a formula (I):
the structure of the star-shaped block macromolecular green plasticizer (I) is composed of three parts: the first is an inner core connected with a star-shaped macromolecular arm through a multifunctional group; the polylactic acid PLA block inner arm is directly connected with the inner core; and the third is the outer arm of the PCL block of the polycyclocaprolactone connected with the PLA block.
The inner core at least contains three functional group atoms X connected with PLA, wherein X is oxygen or nitrogen, the number of X is t +2, and t is an integer more than or equal to 1.
The inner arm is a PLA hard block with high glass transition temperature, the polymerization degree of the PLA hard block is m, and m is 10-40; the outer arm is a PCL soft block with low glass transition temperature, the polymerization degree of the PCL soft block is n, and n is 10-160.
Preferably, m is 20 to 30, and n is 40 to 60.
The PLA blocks are mixed PLA, levorotatory PLA and dextrorotatory PLA, wherein the mixed PLA is represented by PDLLA, the levorotatory PLA is represented by PLLA, and the dextrorotatory PLA is represented by PDLA.
Preferably, the PLA blocks are PLLA and PDLA. More preferably, the PLA block is PLLA.
A flexible polyvinyl chloride comprising:
(A) polyvinyl chloride, and
(B) the star-shaped block macromolecule green plasticizer.
The polyvinyl chloride resin composition comprises 40-80 parts by weight of star-shaped block macromolecule green plasticizer, preferably 40-60 parts by weight per 100 parts by weight of polyvinyl chloride.
Naming:
the star block macromolecule is represented by SxyPLAm-b-PCLnWherein S represents star-shaped macromolecule, x represents the arm number of the star-shaped macromolecule (x is more than or equal to 3), y represents the type of PLA (DL, L and D respectively), m represents the polymerization degree of PLA, and n represents the polymerization degree of PCL.
The initial molecule of the star-shaped block macromolecule green plasticizer (I) for forming the inner core can be a micromolecule or a macromolecule containing at least three hydroxyl groups and primary or secondary amine groups, and the micromolecule or the macromolecule is converted into an ester group or an amide group through reaction to be connected with the PLA block. Representative polyhydroxy compounds include, but are not limited to, the following: triethanolamine, glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol, monosaccharides, disaccharides, polysaccharides, polyhydroxy hyperbranched polyglycidyl glycerol, polyhydroxy hyperbranched polyesters and the like; representative polyamino compounds include, but are not limited to, the following: diethylenetriamine, triethylenetetramine, triaminoethylamine, hyperbranched polyethyleneimine, hyperbranched polyamidoamine, hyperbranched polylysine and the like.
The invention is further illustrated by the following specific examples, in which specific experimental procedures or conditions are not indicated, and which may be carried out according to conventional experimental procedures or conditions described in the literature of the polymer synthesis art. All reagents or instruments are not indicated by the manufacturer, and are conventional reagent products or instruments that are commercially available.
Example 1
Star block macromolecule S3DLPLA30-b-PCL60Preparation of (I-1)
Placing 0.149g of redistilled triethanolamine and 6.49g of DL-lactide into a 25mL three-necked flask, replacing with nitrogen, dissolving and stirring uniformly at 120 ℃, heating to 135 ℃, and adding 0.182g of Sn (Oct) into the reaction system by using a syringe2Reacting the solution with toluene (the concentration is 10 percent) for 24 hours, cooling to room temperature, adding tetrahydrofuran for dissolving, respectively settling with a methanol water solution (the volume ratio of methanol to water is 1: 3) and an ether and petroleum ether solution (the volume ratio of ether to petroleum ether is 1: 3), centrifuging, collecting precipitates, and drying in a vacuum drying oven at 60 ℃ for 24 hours to obtain a polymer S3DLPLA30。
Take 1.20g S3DLPLA30And 3.93g of CL were placed in a single-neck flask, and 0.150g of Sn (Oct) was added2Reacting the toluene solution (the concentration is 10%) at 135 ℃ for 24 hours, cooling, adding tetrahydrofuran for dissolving, respectively settling by using a methanol water solution (the volume ratio of methanol to water is 1: 3) and an ether and petroleum ether solution (the volume ratio of ether to petroleum ether is 1: 3), centrifuging, and drying in a vacuum drying oven at 60 ℃ for 24 hours to obtain the plasticizer I-1. The hydrogen spectrum of I-1 is shown in FIG. 1, in which it can be clearly seen that the characteristic peak of methine group of PLA segment is located in the vicinity of 5.1ppm, and the characteristic peak of methylene group linked to ester bond in PCL segment is located in the vicinity of 4.0 ppm. The spectrogram fully indicates the successful preparation of the star-shaped block macromolecule I-1.
The preparation reaction formula of I-1 is as follows:
example 2
Star block macromolecule S3LPLA30-b-PCL60Preparation of (I-2)
0.149g of redistilled triethanolamine and 6.49g L-lactide was put in a 25mL three-necked flask, replaced with nitrogen, dissolved and stirred at 120 ℃ and heated to 135 ℃ to add 0.182g of Sn (Oct) to the reaction system with a syringe2Reacting the solution with toluene (the concentration is 10 percent) for 24 hours, cooling to room temperature, adding tetrahydrofuran for dissolving, respectively settling with a methanol water solution (the volume ratio of methanol to water is 1: 3) and an ether and petroleum ether solution (the volume ratio of ether to petroleum ether is 1: 3), centrifuging, collecting precipitates, and drying in a vacuum drying oven at 60 ℃ for 24 hours to obtain a polymer S3LPLA30。
Take 1.20g S3LPLA30And 3.93g of CL were placed in a single-neck flask, and 0.150g of Sn (Oct) was added2Reacting the toluene solution (the concentration is 10%) at 135 ℃ for 24 hours, cooling, adding tetrahydrofuran for dissolving, respectively settling by using a methanol water solution (the volume ratio of methanol to water is 1: 3) and an ether and petroleum ether solution (the volume ratio of ether to petroleum ether is 1: 3), centrifuging, and drying in a vacuum drying oven at 60 ℃ for 24 hours to obtain the plasticizer I-2. .
Example 3
Star-shaped block macromolecule S6LPLA30-b-PCL60Preparation of (I-3)
Placing 50.8mg of dipentaerythritol and 2.59g L-lactide in a 25mL three-necked flask, replacing with nitrogen, dissolving at 120 deg.C, stirring, heating to 135 deg.C, adding 72.9mg of Sn (Oct) into the reaction system with a syringe2Reacting the solution with toluene (the concentration is 10 percent) for 24 hours, cooling to room temperature, adding tetrahydrofuran for dissolving, respectively settling with a methanol water solution (the volume ratio of methanol to water is 1: 3) and an ether and petroleum ether solution (the volume ratio of ether to petroleum ether is 1: 3), centrifuging, collecting precipitates, and drying in a vacuum drying oven at 60 ℃ for 24 hours to obtain a polymer S6LPLA30。
Take 0.80g S6LPLA30And 2.25g of CL were placed in a single-neck flask, and 86.1mg of Sn (Oct) were added2Reacting the toluene solution (with the concentration of 10%) at 135 ℃ for 24 hours, cooling, adding tetrahydrofuran for dissolving, and respectively settling with a methanol water solution (the volume ratio of methanol to water is 1: 3) and an ether and petroleum ether solution (the volume ratio of ether to petroleum ether)Is 1: 3) and centrifuging and drying in a vacuum drying oven at 60 ℃ for 24 hours to obtain the plasticizer I-3.
Example 4
Star-shaped block macromolecule S21LPLA30-b-PCL60Preparation of (I-4)
Placing 56.7mg of beta-cyclamine, 2.27g L-lactide and 27.0mg of dimethylaminopyridine into a 25mL three-necked flask, replacing with nitrogen, dissolving at 120 ℃, stirring uniformly, heating to 135 ℃, adding 63.8Sn (Oct) into the reaction system by using a syringe2Reacting the solution with toluene (the concentration is 10 percent) for 24 hours, cooling to room temperature, adding tetrahydrofuran for dissolving, respectively settling with a methanol water solution (the volume ratio of methanol to water is 1: 3) and an ether and petroleum ether solution (the volume ratio of ether to petroleum ether is 1: 3), centrifuging, collecting precipitates, and drying in a vacuum drying oven at 60 ℃ for 24 hours to obtain the scleromere polymer S21 LPLA30。
Take 1.20g S21 LPLA30And 5.88g CL in a one-neck flask, 0.225g Sn (Oct)2Reacting the toluene solution (the concentration is 10%) at 135 ℃ for 24 hours, cooling, adding tetrahydrofuran for dissolving, respectively settling by using a methanol water solution (the volume ratio of methanol to water is 1: 3) and an ether and petroleum ether solution (the volume ratio of ether to petroleum ether is 1: 3), centrifuging, and drying in a vacuum drying oven at 60 ℃ for 24 hours to obtain the plasticizer I-4.
Example 5
Preparation of star block macromolecule plasticized PVC
0.20g of the PVC pellets and 0.12g of the plasticizer were dissolved in 4mL of tetrahydrofuran, stirred for 12h, the clear solution was transferred to a tetrafluoro mold, volatilized at room temperature for 24h, transferred to a 60 ℃ vacuum oven for 24h, and left at room temperature for 24h to prepare a test film having a thickness of about 50 μm. Tensile properties were measured on PVC films using a universal tester according to ASTM D638-2003 with a tensile rate of 20mm/min, and the data are shown in Table 1 below. The plasticized PVC films were separately subjected to leaching tests after 2h dissolution in n-hexane at 50 ℃ according to ASTM D5227-95, to obtain the mobilities, see Table 1. Compared with commercial DEHP plasticized PVC products, PVC products plasticized by the same amount of I-1 to I-4 have more excellent elongation at break and higher toughness, and the plasticizer has higher migration resistance, so that the PVC products are safer and more environment-friendly and are more suitable for application in the biomedical field.
TABLE 1 Properties of plasticized PVC
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (10)
1. A star block macromolecule green plasticizer for soft polyvinyl chloride is characterized by being represented by a formula (I):
the structure of the star-shaped block macromolecular green plasticizer (I) is composed of three parts: the first is an inner core connected with a star-shaped macromolecular arm through a multifunctional group; the polylactic acid PLA block inner arm is directly connected with the inner core; and the third is the outer arm of the PCL block of the polycyclocaprolactone connected with the PLA block.
2. The star block macromolecule green plasticizer for flexible polyvinyl chloride according to claim 1, wherein said core contains at least three atoms X of functional groups linked to PLA, X being oxygen or nitrogen, and the number of X being t +2, t being an integer greater than or equal to 1.
3. The star-block macromolecular green plasticizer for soft polyvinyl chloride according to claim 1, characterized in that said inner arm is a PLA hard block with high glass transition temperature, and its polymerization degree is m, m is 10-40; the outer arm is a PCL soft block with low glass transition temperature, the polymerization degree of the PCL soft block is n, and n is 10-160.
4. The star block macromolecule green plasticizer for flexible polyvinyl chloride according to claim 3, wherein m is 20 to 30, and n is 40 to 60.
5. The star block macromolecular green plasticizer for soft polyvinyl chloride according to claim 1, wherein said PLA block is blend PLA, levorotation PLA, dextrorotation PLA, wherein blend PLA is represented by PDLLA, levorotation PLA is represented by PLLA, dextrorotation PLA is represented by PDLA.
6. The star block macromolecular green plasticizer for flexible polyvinyl chloride according to claim 5, characterized in that said PLA blocks are PLLA and PDLA.
7. The star block macromolecular green plasticizer for flexible polyvinyl chloride according to claim 6, characterized in that said PLA block is PLLA.
8. A flexible polyvinyl chloride comprising:
(A) polyvinyl chloride, and
(B) the star block macromolecular green plasticizer according to any one of claims 1 to 7.
9. The flexible polyvinyl chloride according to claim 8, wherein the polyvinyl chloride contains 40 to 80 parts by weight of the star block macromolecular green plasticizer per 100 parts by weight of the polyvinyl chloride.
10. The flexible polyvinyl chloride according to claim 9, comprising 40 to 60 parts by weight of the star-block macromolecular green plasticizer per 100 parts by weight of the polyvinyl chloride.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104045984A (en) * | 2014-05-22 | 2014-09-17 | 中国科学院长春应用化学研究所 | Polylactic acid stereoscopic complex and preparation method thereof |
| CN105778338A (en) * | 2016-03-25 | 2016-07-20 | 上海天原集团胜德塑料有限公司 | Environment-friendly soft polyvinyl chloride granules |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104045984A (en) * | 2014-05-22 | 2014-09-17 | 中国科学院长春应用化学研究所 | Polylactic acid stereoscopic complex and preparation method thereof |
| CN105778338A (en) * | 2016-03-25 | 2016-07-20 | 上海天原集团胜德塑料有限公司 | Environment-friendly soft polyvinyl chloride granules |
Non-Patent Citations (1)
| Title |
|---|
| DEOKAR MEGHA D.等: ""Synthesis and characterization of well-defined random and block copolymers of ε-caprolactone with L-lactide as an additive for toughening polylactide: Influence of the molecular architecture"" * |
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