CN109337051A - A kind of polyvinyl chloride-polyester copolymer plasticizer and preparation method thereof - Google Patents
A kind of polyvinyl chloride-polyester copolymer plasticizer and preparation method thereof Download PDFInfo
- Publication number
- CN109337051A CN109337051A CN201810981837.7A CN201810981837A CN109337051A CN 109337051 A CN109337051 A CN 109337051A CN 201810981837 A CN201810981837 A CN 201810981837A CN 109337051 A CN109337051 A CN 109337051A
- Authority
- CN
- China
- Prior art keywords
- pvc
- molar ratio
- poly
- monomer
- pcl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The present invention relates to a kind of polyvinyl chloride-polyester copolymer plasticizer and preparation method thereof, more specifically, the present invention relates to one kind to be copolymerized obtained linear and star block copolymer by δ-valerolactone (VL) or 6-caprolactone (CL) and vinyl chloride (VC), it can be used as macromolecular plasticizer, the characteristic that this macromolecular plasticizer has good plasticizing effect and do not move out from matrix, this plasticizer can also be used as the compatilizer of polyvinyl chloride/poly- δ-valerolactone or poly-epsilon-caprolactone blend, reduce or eliminate poly- δ-valerolactone or the problem of moving out of poly-epsilon-caprolactone in polyvinyl chloride/poly- δ-valerolactone or polyvinyl chloride/poly-epsilon-caprolactone system.
Description
Technical field
The present invention relates to a kind of polyvinyl chloride-polyethylene terephthalate copolymer species plasticizer for polyvinyl chloride (PVC) resin and its
Preparation method.More particularly it relates to a kind of total by δ-valerolactone (VL) or 6-caprolactone (CL) and vinyl chloride (VC)
Poly- obtained linear and star block copolymer, can be used as macromolecular plasticizer, and this macromolecular plasticizer has good
Plasticizing effect and the characteristic do not moved out from matrix, this plasticizer can also be used as the phase of polyvinyl chloride and polyester blend
Hold agent, reduces or eliminates poly- δ-valerolactone or poly- ε-in polyvinyl chloride/poly- δ-valerolactone or polyvinyl chloride/poly-epsilon-caprolactone system
The problem of moving out of caprolactone.
Background technique
Polyvinyl chloride is a kind of with extensive thermoplastic, is used for medical material, toy, cable, packing timber
Material, finishing material, construction material and automobile component etc..However polyvinyl chloride is a kind of rigid plastics, general polyvinyl chloride
For glass transition temperature at 80 DEG C or so, which has limited it to be widely applied.By the way that plasticizer is added, polyvinyl chloride can be made
Glass transition temperature significantly reduces, and after general plasticizer additive amount reaches 30-50%, polyvinyl chloride can be from hard
Be changed into it is soft, to allow to apply to the fields such as packaging bag, blood bag and bag filter.What is be widely used at present is poly-
Vinyl chloride plasticizer is phthalate compound, wherein most commonly seen with dioctyl phthalate (DOP).This kind of
Plasticizer due to plasticizing efficiency is high, at low cost and simple process and widely used, however as going deep into for research, Ren Menfa
Existing this kind of plasticizer is easy to move out from matrix, on the one hand affects the effect of plasticising, the plasticizer on the other hand moved out is such as
Fruit enters internal, it will the body for bringing some harm to the kidney of people and reproductive system etc. and influencing the especially children of people is good for
Health, so by disabling gradually, the plasticizer for finding alternative environment-friendly type becomes phthalic ester plasticizer now
The task of top priority.
Macromolecular plasticizer is compared with this small molecule plasticizer of phthalate, because may with polyvinyl chloride
The entanglement and interaction between segment are generated, so extent of migration will be greatly reduced, but this macromolecular plasticizer is also deposited
In some problems, one side speedup efficiency can have substantial degradation, on the other hand usually due to macromolecular plasticizer generally
It is the substance of polyester and polyethers, these substances can't reach the degree fully compatible with PVC base system, so making
Still have in it is certain move out, so the problem of migration can not be fully solved.
Summary of the invention
It is an object of the invention to prepare a kind of novel polyesters plasticizer containing polyvinyl chloride segment, with good
Good plasticization effect, while polyvinyl chloride segment therein can be fully compatible with polyvinyl chloride, to solve plasticizer
The problem of moving out.This plasticizer is also used as polyvinyl chloride and the compatilizer of polyester blend uses.
The linear and star block copolymer that the δ-valerolactone or 6-caprolactone and chloroethylene copolymer obtains shares six
Kind, structural formula is as follows:
Including linear copolymer PVC-b-PVL and PVC-b-PCL；Three-arm star-shaped block copolymer PVC-star-
(PVL)2With PVC-star- (PCL)2；Four arm star block copolymers (PVC)2-star-(PVL)2(PVC)2-star-
(PCL)2.The degree of polymerization m=30 of polymerization degree n=80~1600 of polyvinyl chloride section, poly- δ-valerolactone or 6-caprolactone section~
400。
The linear and star block copolymer for preparing above-mentioned δ-valerolactone or 6-caprolactone and vinyl chloride has following three kinds
Method:
Method 1 first synthesizes PVC sections of polymer, then synthesizes PVL or PCL sections of polymer.Solvent, VC are added in autoclave
Monomer, corresponding RAFT reagent and initiator, wherein the molar ratio of solvent and VC monomer is 1:1~4:1, monomer and corresponding RAFT
The molar ratio of reagent is 80:1~400:1, and the molar ratio of corresponding RAFT reagent and initiator is 10:1~1:1, at 40~60 DEG C
24~60h of lower reaction, the available polyvinylchloride-OH with hydroxy functional group after product is precipitated in methyl alcohol.Then
Take PVC-OH, VL or CL, ring-opening reaction catalyst such as diphenyl phosphate (DPP) and solvent are placed in polymerization pipe, solvent and VL or
The molar ratio of CL monomer is that the molar ratio of 1:1~4:1, PVC-OH and VL or CL are 1:10~1:500, VL or CL and ring-opening reaction
The molar ratio of catalyst is 5:1~100:1, and 6~8h is reacted at 20~60 DEG C, after reaction precipitates product in methyl alcohol
The linear and star block copolymer that available δ-valerolactone or 6-caprolactone and polyvinyl chloride are copolymerized afterwards.
Method 2 first synthesizes PVL or PCL sections of polymer, then synthesizes PVC sections of polymer.By RAFT reagent, VL or CL monomer,
Ring-opening reaction catalysts and solvents are placed in polymerization pipe, the molar ratio of solvent and VL or CL monomer be 1:1~4:1, VL or CL and
The molar ratio of RAFT reagent is 10:1~800:1, VL or CL and the molar ratio of ring-opening reaction catalyst is 5:1~100:1,
6~8h is reacted at 20~60 DEG C, it is available with PVL or PCL sections of polymerization after after reaction precipitating product in methyl alcohol
The Macro RAFT agent of object.Then solvent, VC monomer, the macromolecular with PVL or PCL sections of polymer are added in autoclave
RAFT reagent and initiator, wherein the molar ratio of solvent and VC monomer be 1:1~4:1, VC monomer and Macro RAFT agent
Molar ratio be 400:1~1800:1, the molar ratio of corresponding Macro RAFT agent and initiator is 10:1~1:1,40~
24~80h is reacted at 60 DEG C, available δ-valerolactone or 6-caprolactone are total to polyvinyl chloride after product is precipitated in methyl alcohol
Poly- obtained linear and star block copolymer.
Method 3, PVC sections of polymer of one pot process and PVL or PCL sections of polymer.Solvent is added in autoclave, VC is mono-
Body, VL or CL monomer, corresponding RAFT reagent, initiator and ring-opening reaction catalyst, the wherein molar ratio of solvent and VC monomer
Molar ratio for 1:1~4:1, VC and VL or CL monomer is the molar ratio of 0.1:1~9:1, VL or CL and ring-opening reaction catalyst
For 5:1~100:1, the molar ratio of VC monomer and corresponding RAFT reagent is 80:1~400:1, corresponding RAFT reagent and initiator
Molar ratio is 10:1~1:1,24~60h is reacted at 40~60 DEG C, after product is precipitated in methyl alcohol in available δ-penta
The linear and star block copolymer that ester or 6-caprolactone and polyvinyl chloride are copolymerized.
Solvent in three kinds of preparation methods includes tetrahydrofuran (THF), the organic solvents such as dioxane.
RAFT reagent in three kinds of preparation methods includes the change of linear, three arms and four armband hydroxyls xanthic acid esters
Close object.
Initiator in three kinds of preparation methods includes azodiisobutyronitrile (AIBN), azobisisoheptonitrile (ABVN) etc.
Azo-initiator.
The linear and star block copolymer that δ-valerolactone or 6-caprolactone of the present invention and chloroethylene copolymer obtain,
It can be used directly as PVC plasticizer, the compatilizer that can also be used as blend uses.Specifically, in PVC/PVL or
Additive amount block copolymer in PVC/PCL blend, the i.e. plasticizer of PVC-PVL type can be used in PVC/PVL co-mixing system,
PVL therein is set to be not easy to move out from co-mixing system；Equally, the plasticizer of PVC-PCL type can be used for PVC/PCL blending
In system, PCL therein is made to be not easy to move out from co-mixing system, when PCL or PVL mass ratio is greater than 1:50, so that it may so that former
PVL or PCL polymer may move out in use is no longer moved out, so that making blend also can have without the characteristic moved out,
Guarantee the performance of polymer blend.
Plasticizer performance measures glass transition temperature by DSC method and evaluates in the present invention, by measure different PVL or
The glass transition temperature of the block copolymer of PCL content, to evaluate the effect of plasticizer.
Plasticizer of the present invention is plasticized performance by the elongation at break of tension test measurement PVC sample to PVC to evaluate.It will
After PVC and plasticizer are blended, mini tensile bars are made, tension test is carried out by universal testing machine, passes through stretching
Intensity and elongation at break evaluate last plasticization effect.
The method moved out of the plasticizer of the present invention in PVC is extracting experiment, i.e., PVC and plasticizer is dissolved in THF, molten
Film is formed after agent volatilization, takes a certain amount of film to be placed in n-hexane and impregnates, a certain amount of hexamethylene diisocyanate is added
As internal standard, certain solution is just taken to carry out the measurement of infrared spectroscopy, O=C in hexamethylene diisocyanate at regular intervals
=N group has infrared signature absorption peak in 2200-2300, there is red C=O group between 1700-1800 in plasticizer of the present invention
Outer characteristic absorption peak, therefore can be calculated and be moved out by the comparison of the infrared integral area at the peak to O=C=N and C=O
The amount of plasticizer.
The linear and star block copolymer of δ-valerolactone or 6-caprolactone and vinyl chloride of the present invention is as plasticising
Agent is advantageous in that: (1) macromolecular plasticizer asepsis environment-protecting is safe from harm to human body, and will not move in use
Out, will not make because of moving out for plasticizer material property deteriorate or be that health impacts to the mankind；(2) plasticizing efficiency
The comparison of height and DOP show that plasticization effect can be close to even slightly better than DOP generally in the higher situation of amount of polyester
Effect, have a broad prospect of the use；(3) it is used as compatilizer, the utilization of PVL or PCL macromolecular plasticizer can be widened
Range can also improve the effect of PVC/PVL or PVC/PCL blend, obtain PVL the or PCL component in blend non-migratory
Effect.
Detailed description of the invention
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of RAFT reagent RAFT-1 used in line polymer；
Fig. 2 is the nucleus magnetic hydrogen spectrum figure of line polymer PVC-b-PVL and PVC-b-PCL；
Fig. 3 is the nucleus magnetic hydrogen spectrum figure of RAFT reagent RAFT-2 used in three arm star shape polymer；
Fig. 4 is three arm star shape block polymer PVC-star- (PCL)2Nucleus magnetic hydrogen spectrum figure；
Fig. 5 is the nucleus magnetic hydrogen spectrum figure of RAFT reagent RAFT-3 used in four arm star shape polymer；
Fig. 6 is four arm star shape block polymers (PVC)2-star-(PVL)2Nucleus magnetic hydrogen spectrum figure；
Fig. 7 is four arm star shape block polymers (PVC)2-star-(PCL)2Nucleus magnetic hydrogen spectrum figure；
Fig. 8 is the DSC figure of the PVC-b-PCL block copolymer of different PCL contents；
Fig. 9 is DOP, (PVC)2-star-(PVL)2(PVC)2-star-(PCL)2Stress-after sample plasticized PVC is answered
Become figure；
Figure 10 is that plasticizer of the present invention impregnates the curve graph of moving out after 40h in n-hexane；
Figure 11 is the infrared spectrum that plasticizer of the present invention is applied in terms of PVC/PCL compatilizer.
Specific embodiment
Illustrate technical solutions and effects of the present invention by way of specific embodiment below, but the present invention and unlimited
In following embodiment.
Embodiment 1:
In autoclave be added THF solvent (23.0g, 320mmol), VC monomer (20.0 g, 320mmol), THF solvent and
The molar ratio of VC monomer be 1:1, with a hydroxyl linear xanthic acid esters RAFT reagent RAFT-1 (0.9g, 3.8mmol,
Structural formula and nuclear magnetic resonance1H NMR spectra is shown in Fig. 1), the molar ratio of monomer and corresponding RAFT reagent is 84.2:1, initiator
The molar ratio of ABVN (0.1g, 0.4mmol), RAFT reagent and initiator is 9.5:1,60h is reacted at 50 DEG C, by product in first
Available polyvinylchloride-the OH with hydroxy functional group after being precipitated in alcohol.Then PVC-OH (1.0g, 0.1 mmol) is taken,
Monomer VL (1.0g, 10mmol) or CL (1.2g, 10mmol), catalyst DPP (0.5g, 2mmol) and THF solvent (1.0g,
It 14mmol) is placed in polymerization pipe, the molar ratio of THF solvent and VL or CL monomer is mole of 1.4:1, PVC-OH and VL or CL
Than being 5:1 for the molar ratio of 1:100, VL or CL and DPP, 7h is reacted at 50 DEG C, product sinks in methyl alcohol after reaction
Available PVC-b-PVL and PVC-b-PCL shape block copolymer (structural formula and nuclear magnetic resonance behind shallow lake1H NMR spectra is shown in
Fig. 2).PVC polymerization degree n=160, PVL degree of polymerization m=65 in PVC-b-PVL in the present embodiment；PVC polymerize in PVC-b-PCL
Spend n=160, PCL degree of polymerization m=55.
Embodiment 2:
By band, there are two three-arm star-shaped xanthic acid esters RAFT reagent RAFT-2 (structural formula and the nuclear magnetic resonance of hydroxyl1H
NMR spectra is shown in Fig. 3) RAFT reagent (0.25g, 0.8mmol), CL monomer (73.0g, 640mmol), DPP (2.0g, 8mmol) and
Dioxane (220.0g, 2.5mol) solvent is placed in polymerization pipe, and the molar ratio of dioxane solvent and CL monomer is 3.9:
The molar ratio of 1, CL and RAFT reagent is that the molar ratio of 800:1, CL and DPP are 80:1, reacts 8h at 60 DEG C, after reaction
The available Macro RAFT agent with PCL sections of polymer after product is precipitated in methyl alcohol.Then add in autoclave
Enter THF solvent (105.0g, 1.2mol), VC monomer (18.5g, 300mmol), the macromolecular with PCL sections of polymer
The molar ratio of RAFT reagent (18.2g, 0.2mmol) and initiator A IBN (0.03g, 0.2mmol), THF solvent and VC monomer is
The molar ratio of 4:1, VC monomer and Macro RAFT agent is 1500:1, the molar ratio of corresponding Macro RAFT agent and initiator
For 1:1,80h is reacted at 40 DEG C, the 6-caprolactone of available three arm star and polychlorostyrene second after product is precipitated in methyl alcohol
Alkene block copolymer PVC-star- (PCL)2(structural formula and nuclear magnetic resonance1H NMR spectra is shown in Fig. 4).PVC- in the present embodiment
star-(PCL)2Middle PVC polymerization degree n=1400, PCL degree of polymerization m=400.
Embodiment 3:
THF solvent (86.5g, 1.2mol) is added in autoclave, VC monomer (30.0g, 480mmol), VL (80.0g,
800mmol) or CL (45g, 400mmol) monomer, the molar ratio of THF solvent and VC monomer is 2.5:1, VC and VL monomer rubs
You are than being 0.6:1, and the molar ratio of VC and CL monomer is 1.2:1, and there are two four arm stars of hydroxyl and two xanthate groups for band
Shape xanthic acid esters RAFT reagent RAFT-3 (0.6g, 1.2mmol, structural formula and nuclear magnetic resonance1H NMR spectra is shown in Fig. 5), VC is mono-
The molar ratio of body and corresponding RAFT reagent is 400:1, initiator A BVN (0.04g, 0.16mmol), RAFT reagent and initiator
Molar ratio is 7.5:1, and the molar ratio of DPP (5g, 20mmol), VL and DPP are that the molar ratio of 40:1, CL and DPP are 20:1,55 DEG C
Lower reaction 30h, the δ-valerolactone of available four arm star and 6-caprolactone and polyvinyl chloride after product is precipitated in methyl alcohol
Block copolymer (PVC)2-star-(PVL)2(PVC)2-star-(PCL)2(structural formula and nuclear magnetic resonance1H NMR spectra is shown in figure
6 and Fig. 7).In the present embodiment (PVC)2-star-(PVL)2Middle PVC polymerization degree n=200, PVL degree of polymerization m=400；(PVC)2-
star-(PCL)2Middle PVC polymerization degree n=200, PCL degree of polymerization m=200.
Embodiment 4:
The PVC-b-PCL synthesized in embodiment 1 prepares a series of different block copolymer of PCL contents, uses dsc measurement
Glass transition is shown in Fig. 8 thus come the PCL content of plasticizer required for determining.It can be seen from the figure that working as block polymerization
When PCL content is higher than 60% in object, the glass transition temperature of block polymer can be reduced to 0 DEG C hereinafter, this just directly can be with
As good plasticizer.
Embodiment 5:
(PVC) synthesized in embodiment 32-star-(PVL)2(PVC)2-star-(PCL)2, tetrahydro is dissolved in PVC
In furans, film is formed after tetrahydrofuran volatilization, mini batten is made in film, is then drawn using universal testing machine
Test is stretched, tensile strength and elongation at break is recorded, sees Figure 10.It can be seen from the figure that (PVC)2-star-(PVL)2Plasticizer
Compared with DOP, PVL sections of addition makes the tensile strength of sample increase, but elongation at break is slightly less than the value of DOP；
(PVC)2-star-(PCL)2For plasticizer compared with DOP, tensile strength is also to increase, but elongation at break is higher, it was demonstrated that
Macromolecular plasticizer in the present invention also has a good plasticization effect.
Embodiment 6:
The PVC-b-PCL synthesized in embodiment 1, is dissolved in tetrahydrofuran with PVC, is formed after tetrahydrofuran volatilization thin
Film takes a certain amount of film to be placed in n-hexane and impregnates, and a certain amount of hexamethylene diisocyanate is added as internal standard, use is infrared
The situation of moving out of plasticizer at any time is measured, sees Figure 11.It can be seen from the figure that general DOP plasticizer is just moved out in 10h
80% or more, and the PVC-b-PCL macromolecular plasticizer synthesized after 40h still without migrating out, illustrate the present invention
The macromolecular plasticizer of synthesis has the characteristics that non-migratory.
Embodiment 7:
The PVC-star- (PCL) synthesized in embodiment 220.06g adds PVC and PCL (PVC/PCL=7/3, quality
Than) blend 10g, PVC-star- (PCL)2Mass ratio with PCL is 1:50.It can with the result compared after addition before addition
To find out, after adding block copolymer, the PCL to move out at any time originally no longer moves out now, and showing the block polymer can
Using the effect as PVC/PCL compatilizer.
Claims (8)
1. a kind of PVC plasticizer, which is characterized in that being includes polyvinyl chloride section and poly- δ-valerolactone section is linear or starblock is total
Polymers, or the linear or star block copolymer including polyvinyl chloride section and poly-epsilon-caprolactone section, structural formula are as follows:
1.(a)PVC-b-PVL；(b)PVC-b-PCL
2.(a)PVC-star-(PVL)2；(b)PVC-star-(PCL)23.(a)(PVC)2-star-(PVL)2；(b)(PVC)2-
star-(PCL)2
Wherein k=1, poly (δ-VL) (PVL)；K=2, poly (ε-CL) (PCL)
N=80~1600；M=30~400.
2. preparing a kind of method of plasticizer as described in claim 1, which is characterized in that first synthesize PVC sections of polymer, then close
At PVL or PCL sections of polymer；Solvent, VC monomer, corresponding RAFT reagent and initiator are added in autoclave, wherein solvent
Molar ratio with VC monomer is 1: 1~4: 1, and the molar ratio of monomer and corresponding RAFT reagent is 80: 1~400: 1, corresponding RAFT examination
The molar ratio of agent and initiator is 10: 1~1: 1, and 24~60h is reacted at 40~60 DEG C, after product is precipitated in methyl alcohol
To the polyvinylchloride-OH for having hydroxy functional group；Then PVC-OH, VL or CL are taken, ring-opening reaction catalysts and solvents are placed in
In polymerization pipe, the molar ratio that the molar ratio of solvent and VL or CL monomer is 1: 1~4: 1, PVC-OH and VL or CL is 1: 10~1:
The molar ratio of 500, VL or CL and ring-opening reaction catalyst is 5: 1~100: 1,6~8h is reacted at 20~60 DEG C, reaction terminates
It is embedding that the linear or star that δ-valerolactone or 6-caprolactone and polyvinyl chloride are copolymerized is obtained after product is precipitated in methyl alcohol afterwards
Section copolymer.
3. preparing a kind of method of plasticizer as described in claim 1, which is characterized in that first synthesize PVL or PCL sections of polymerization
Object, then synthesize PVC sections of polymer；By RAFT reagent, VL or CL monomer, ring-opening reaction catalysts and solvents are placed in polymerization pipe,
The molar ratio of solvent and VL or CL monomer be 1: 1~4: 1, VL or the molar ratio of CL and RAFT reagent be 10: 1~800: 1, VL or
The molar ratio of CL and ring-opening reaction catalyst is 5: 1~100: 1,6~8h is reacted at 20~60 DEG C, after reaction by product
The Macro RAFT agent with PVL or PCL sections of polymer is obtained after precipitating in methyl alcohol；Then it is added in autoclave molten
Agent, VC monomer, the RAFT reagent and initiator of the macromolecular with PVL or PCL sections of polymer, wherein solvent and VC monomer rub
You are 400: 1~1800: 1 than the molar ratio for being 1: 1~4: 1, VC monomer and Macro RAFT agent, corresponding macromolecular RAFT examination
The molar ratio of agent and initiator is 10: 1~1: 1, and 24~80h is reacted at 40~60 DEG C, after product is precipitated in methyl alcohol
The linear or star block copolymer being copolymerized to δ-valerolactone or 6-caprolactone and polyvinyl chloride.
4. preparing a kind of method of plasticizer as described in claim 1, which is characterized in that PVC sections of polymer of one pot process
With PVL or PCL sections of polymer；Solvent, VC monomer, VL or CL monomer, corresponding RAFT reagent, initiation are being added in autoclave
Agent and ring-opening reaction catalyst, wherein the molar ratio of solvent and VC monomer is the molar ratio of 1: 1~4: 1, VC and VL or CL monomer
Molar ratio for 0.1: 1~9: 1, VL or CL and ring-opening reaction catalyst is 5: 1~100: 1, VC monomer and corresponding RAFT reagent
Molar ratio be 80: 1~400: 1, the molar ratio of corresponding RAFT reagent and initiator is 10: 1~1: 1, anti-at 40~60 DEG C
Answer 24~60h, obtained after product is precipitated in methyl alcohol δ-valerolactone or 6-caprolactone be copolymerized with polyvinyl chloride it is linear
Or star block copolymer.
5. the method as described in claim 2-4 any one, which is characterized in that solvent is selected from tetrahydrofuran or dioxane.
6. the method as described in claim 2-4 any one, which is characterized in that the RAFT reagent is selected from linear, three arm stars
The compound of shape or the hydroxyl xanthic acid esters of four arm stars.
7. the method as described in claim 2-4 any one, which is characterized in that the initiator is selected from azodiisobutyronitrile
Or azobisisoheptonitrile.
8. a kind of purposes of plasticizer described in claim 1, which is characterized in that this plasticizer is used for polyethylene and poly- δ-penta
The compatilizer of lactone or poly-epsilon-caprolactone blend, reduce or eliminate polyvinyl chloride/poly- δ-valerolactone or polyvinyl chloride/poly- ε-oneself
Poly- δ-valerolactone or the problem of moving out of poly-epsilon-caprolactone in lactone system, and the additive amount of plasticizer and poly- δ-valerolactone or
It is 1: 50 or more that the ratio of poly- ε-caprolactone, which reaches mass ratio, make poly- δ-valerolactone in corresponding co-mixing system or poly- ε-oneself
Lactone achievees the effect that not move out.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810981837.7A CN109337051B (en) | 2018-08-27 | 2018-08-27 | Polyvinyl chloride-polyester copolymer plasticizer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810981837.7A CN109337051B (en) | 2018-08-27 | 2018-08-27 | Polyvinyl chloride-polyester copolymer plasticizer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109337051A true CN109337051A (en) | 2019-02-15 |
| CN109337051B CN109337051B (en) | 2020-06-26 |
Family
ID=65291632
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810981837.7A Active CN109337051B (en) | 2018-08-27 | 2018-08-27 | Polyvinyl chloride-polyester copolymer plasticizer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109337051B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140116749A1 (en) * | 2012-10-31 | 2014-05-01 | Polyone Corporation | Use of polycaprolactone plasticizers in poly(vinyl chloride) compounds |
-
2018
- 2018-08-27 CN CN201810981837.7A patent/CN109337051B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140116749A1 (en) * | 2012-10-31 | 2014-05-01 | Polyone Corporation | Use of polycaprolactone plasticizers in poly(vinyl chloride) compounds |
Non-Patent Citations (5)
| Title |
|---|
| JEONGSOO CHOI ET AL: ""Hyperbranched Poly(ε-caprolactone) as a Nonmigrating Alternative Plasticizer for Phthalates in Flexible PVC"", 《ENVIRON. SCI. TECHNOL.》 * |
| KYU WON LEE ET AL: ""Highly Branched Polycaprolactone/Glycidol Copolymeric Green Plasticizer by One-Pot Solvent-Free Polymerization"", 《ACS SUSTAINABLE CHEM. ENG.》 * |
| PAOLO FERRUTI ET AL: ""Polycaprolactone-Poly(ethylene glycol) Multiblock Copolymers as Potential Substitutes for Di(ethylhexyl) Phthalate in Flexible Poly(vinyl chloride) Formulations"", 《BIOMACROMOLECULES》 * |
| RUDOLPH D ET AL: ""Polycaprolactone as a Permanent Plasticizer for Poly(vinyl chloride)"", 《JOURNAL OF VINYL TECHNOLOGY》 * |
| XUDONG LOU ET AL: ""Living Cationic Polymerization of δ-Valerolactone and Synthesis of High Molecular Weight Homopolymer and Asymmetric Telechelic and Block Copolymer"", 《MACROMOLECULES》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109337051B (en) | 2020-06-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Vandenberg | Epoxide polymers: Synthesis, stereochemistry, structure, and mechanism | |
| CN104910329B (en) | A kind of polar cyclic olefin copolymer and preparation method thereof | |
| US9217056B2 (en) | Polymers, the process for the synthesis thereof and compositions comprising same | |
| CN109293857B (en) | Polyvinyl chloride-based additive and preparation method thereof | |
| US20190315915A1 (en) | New high molecular weight polymers from waste raw materials | |
| CN103951786B (en) | A kind of cyclic olefine copolymer and preparation method thereof | |
| Lusinchi et al. | Recycling of PET and PVC wastes | |
| CN109337051A (en) | A kind of polyvinyl chloride-polyester copolymer plasticizer and preparation method thereof | |
| CN117004007B (en) | Crystalline aliphatic polycarbonate with high molecular weight and high mechanical property and preparation method thereof | |
| CN103965402B (en) | A kind of cyclic olefine copolymer and its preparation method | |
| Sepulchre et al. | 300 MHz 1H‐NMR study of poly (propylene sulfide) | |
| CN109575167A (en) | A kind of preparation method and application of polyvinyl chloride | |
| JP2002201327A (en) | High-density and branched structure type aliphatic polyester for plasticizer of pvc and flexible pvc blend containing the same | |
| CN107098997A (en) | A kind of isotactic polypropylene containing ammonium ion is from aggressiveness and preparation method | |
| Kozlowska et al. | Morphology evaluation of biodegradable copolyesters based on dimerized fatty acid studied by DSC, SAXS and WAXS | |
| Cais et al. | Copolymerization of acrylamide with sulphur dioxide. Determination of the effect of copolymerization temperature on the monomer sequence distribution by 13C NMR | |
| CN107474162B (en) | A kind of universal gel-like polyrotaxane crosslinking agent and preparation method thereof | |
| US3522194A (en) | Process for polymerizing olefin oxide | |
| CN106680275A (en) | Method for analyzing polyurethane in polyvinyl chloride system | |
| Segre et al. | Studies on comblike polymers. 7. Carbon-13 NMR characterization of poly (oxiranes) containing long hydrocarbon side chains | |
| CN107176910A (en) | A kind of acetylation citric acid fatty acid ester plasticizer and its preparation method and application | |
| CN109134836B (en) | Polyether ester elastomer capable of being coordinated and crosslinked with metal ions, and preparation method and application thereof | |
| DE68912064T2 (en) | Grafted block copolymers, processes for their preparation and their use. | |
| CN114181381B (en) | Castor oil-based aliphatic-aromatic-polylactic acid copolymer and preparation method thereof | |
| CN107513155B (en) | A kind of biodegradable polyesters and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |