CN112409726A - Hydrophilic polyvinyl chloride compound - Google Patents
Hydrophilic polyvinyl chloride compound Download PDFInfo
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- CN112409726A CN112409726A CN202011338456.0A CN202011338456A CN112409726A CN 112409726 A CN112409726 A CN 112409726A CN 202011338456 A CN202011338456 A CN 202011338456A CN 112409726 A CN112409726 A CN 112409726A
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- polyvinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
Abstract
The present invention relates to a hydrophilic polyvinyl chloride compound. The polyvinyl chloride compound comprises polyvinyl chloride resin and a plasticizer with a structural formula shown as a formula (1), wherein,
in the formula (1), R is selected from-H, or C1-18 straight-chain, branched or cyclic alkyl or O ═ CR2‑、CH2＝C(CH3)‑CH2-one of the above; r1Can be selected from-CH2‑CH2‑、‑CH2‑CH2(CH3)‑、‑CH2‑CH2(CH3) -one of the above; x is selected from 1-100; r2Can be selected from linear, branched or cyclic ones having 4 to 10 carbon atomsAlkyl, which may also be selected from phenyl.
Description
Technical Field
The invention relates to the field of polyvinyl chloride resin compounds, in particular to a hydrophilic polyvinyl chloride compound.
Background
Polyvinyl chloride (PVC) is widely used in disposable medical supplies due to its excellent chemical stability, low price, and more importantly, its good stabilizing effect on erythrocytes, and among medical polymer materials, PVC occupies about 40% of the market. However, the PVC material has high molecular polarity and strong intermolecular force, so that the PVC material is hard and brittle and has poor processability, and therefore, different parts of plasticizer are required to be added to improve the processability, and the PVC material is made into soft and hard products to meet the requirements of different medical markets.
When the polyvinyl chloride material is applied to medical products, the requirements of the material science and the biology are met, such as: 1) PVC medical products need to meet certain mechanical properties; 2) the used plasticizer is non-toxic and cannot migrate out of the PVC matrix; 3) good biocompatibility and no anaphylactic reaction; 4) good blood compatibility, low hemolysis, good anticoagulation and the like.
However, the current medical polyvinyl chloride materials have the following two main problems: 1) during the processing of polyvinyl chloride, a plasticizer is required to be added to improve the processing performance and meet the use requirement of products, but the migration problem of the plasticizer, especially Phthalate (PAEs) plasticizer, brings the risk to human health; 2) due to poor hydrophilicity and biocompatibility of PVC, the hydrophilicity is an important factor influencing the biocompatibility and blood compatibility of medical PVC materials, and is easy to influence the quality of stored blood or cause variation of human tissues in contact with the stored blood. Therefore, the migration of the plasticizer is solved, the hydrophilicity and the biocompatibility of the PVC are improved, and the PVC material has important significance for improving the service performance of the medical PVC material.
Non-patent document 1 reports that a PVC blend prepared by using an amphiphilic block polymer of polyethylene oxide (PEO) and polypropylene oxide (PPO) (PEO-PPO-PEO) as a polymeric plasticizer has good transparency and flexibility, and does not adhere to platelets and has good blood compatibility.
Non-patent document 2 reports that PEG-4000 is grafted on the surface of PVC plastic pipes and sheets, and the surface-grafted PEG greatly reduces the migration of plasticizers. The modified surface has better hydrophilicity and blood compatibility than pure PVC.
In non-patent document 3, allyl polyethylene glycol (APEG) is grafted onto a PVC molecular chain by an ARTP method to obtain a hydrophilic PVC material having a good hydrophilicity (a contact angle is reduced from 81 to 64 °).
In non-patent document 4, polyethylene glycol methyl ether methacrylate (PEGMA) is grafted onto polyether sulfone (PES) to synthesize PES-g-PEGMA, and then PES-g-PEGMA and PVC are solution-blended to obtain a PVC/PES-g-PEGMA blended membrane, and when the ratio of PVC to PES-g-PEGMA is 7:3, the contact angle is reduced from the original 72 degrees to 58 degrees, and good hydrophilicity is exhibited. However, the plasticising properties of PVC blend materials are not evaluated in this document.
Although in the hydrophilic modification of medical polyvinyl chloride materials, various techniques of hydrophilic modification such as blending, grafting, and the like have appeared. However, these methods typically require multi-step processes and multi-component property integration to meet the practical application requirements of medical polyvinyl chloride materials.
Non-patent document 1: leem Kim KO, JuYM, polyethylene de add/-ve-entvapped polyvinyl chloride as a new blood bag material J Biomed Material Res, 1999, 48: 328-334.
Non-patent document 2: lakshmi S, Jayakrishnan a. simulation resistor, block-compatible plastic polyvinyl chloride for media and related applications, artifi Organs, 1998, 22 (3): 222-229.
Non-patent document 3: preparation and film-forming properties of maleic cure, Hanyu, Lu Yin, polyvinyl chloride grafted allyl polyethylene glycol [ J ] macromolecular material science and engineering, 2014,30, 145-one 148.
Non-patent document 4: preparation of Jianshuhong, Xiaomenglin, Yanfan, Wangjun. PVC/PES-g-PEGMA blend membrane and its anti-pollution performance [ J ].2015,9,2310 and 2316.
Disclosure of Invention
Problems to be solved by the invention
In view of the above-mentioned prior art problems, it is an object of the present invention to provide a polyvinyl chloride compound with low or no migration and with good hydrophilicity; further, it is an object of the present invention to provide a polyvinyl chloride compound having improved biocompatibility and reduced biotoxicity.
Means for solving the problems
In order to achieve the above object, the present invention provides an environmentally friendly and nontoxic polyvinyl chloride compound having the following features [1] to [6 ].
[1] A polyvinyl chloride compound comprises polyvinyl chloride resin and a plasticizer with a structural formula shown as a formula (1), wherein,
in the formula (1), R is selected from-H, or C1-18 straight-chain, branched or cyclic alkyl or O ═ CR2-、CH2＝C(CH3)-CH2-one of the above; r1 can be selected from-CH2-CH2-、-CH2-CH2(CH3)-、-CH2-CH2-CH2-CH2-one of the above; x is selected from 1-100; r2The alkyl group may be selected from a linear, branched or cyclic alkyl group having 4 to 10 carbon atoms, and may be selected from a phenyl group.
[2]According to [1]Wherein R in the formula (1) is-H, or a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, or O ═ CR2-、CH2＝C(CH3)-CH2-one of the above.
[3]According to [1]In said formula (1), R1 can be selected from-CH2-CH2-、-CH2-CH2(CH3)-、-CH2-CH2-CH2-CH2-one of the above.
[4] A polyvinyl chloride compound according to [1], wherein in the formula (1), x is selected from 1 to 100.
[5]According to [1]Of formula (1), R2The alkyl group may be selected from phenyl groups, and may be selected from linear, branched or cyclic alkyl groups having 4 to 10 carbon atoms.
[6] The polyvinyl chloride compound according to [1], wherein the plasticizer accounts for 5-80 parts by weight based on 100 parts by weight of the polyvinyl chloride resin.
ADVANTAGEOUS EFFECTS OF INVENTION
The invention provides a transparent nontoxic polyvinyl chloride compound, wherein a plasticizer in the compound has chemical structures of ether bond and ester bond, and when the compound with the chemical structure is used as the plasticizer for plasticizing PVC, the compound has good compatibility with PVC, so that the compound has better transparency, good mechanical property and excellent migration resistance; in addition, the use of the plasticizer molecules of formula (a) provides good biocompatibility and hydrophilicity, which results in articles made from the PVC compounds of the present invention having good biological properties (e.g., no cytotoxicity, good biocompatibility, no coagulation, etc.).
The polyvinyl chloride compound of the invention can be used in various industries where hydrophilicity and suppression of migration of plasticizers are required, and is particularly suitable for use as a medical material.
Detailed Description
The present invention will be described in detail below. The technical features described below are explained based on typical embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples. It should be noted that:
in the present specification, the numerical range represented by "numerical value a to numerical value B" means a range including the end point numerical value A, B.
In the present specification, the meaning of "may" includes both the meaning of performing a certain process and the meaning of not performing a certain process.
Reference throughout this specification to "some particular/preferred embodiments," "other particular/preferred embodiments," "embodiments," or the like, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various embodiments.
< polyvinyl chloride Compound >
The polyvinyl chloride compound comprises polyvinyl chloride resin and a plasticizer with a structural formula shown as a formula (1), wherein,
in the formula (1), R is selected from-H, or C1-18 straight-chain, branched or cyclic alkyl or O ═ CR2-、CH2＝C(CH3)-CH2-one of the above; r1 can be selected from-CH2-CH2-、-CH2-CH2(CH3)-、-CH2-CH2-CH2-CH2-one of the above; x is selected from 1-100; r2The alkyl group may be selected from a linear, branched or cyclic alkyl group having 4 to 10 carbon atoms, and may be selected from a phenyl group.
The content of the plasticizer in the polyvinyl chloride compound is preferably 5 to 80 parts by weight, more preferably 8 to 70 parts by weight, and still more preferably 10 to 60 parts by weight, relative to 100 parts by weight of the polyvinyl chloride resin.
The components and structural units in the polyvinyl chloride compounding of the present invention are described in detail below.
(polyvinyl chloride resin)
The polyvinyl chloride resin in the present invention refers to various polyvinyl chloride resins known in the art, including vinyl chloride homopolymers and copolymers of vinyl chloride monomers and vinyl monomers copolymerizable with the vinyl chloride monomers. In some preferred cases, the copolymer is preferably a copolymer of 50% by weight or more of a vinyl chloride monomer and 50% by weight or less of a vinyl monomer copolymerizable with vinyl chloride. Specific examples include, without limitation: suspension-process polyvinyl chloride resins such as PVC-SG1, PVC-SG2, PVC-SG3, PVC-SG4, PVC-SG5, PVC-SG6, PVC-SG7, PVC-SG8, etc.; emulsion polyvinyl chloride resin; bulk polyvinyl chloride resin; polyvinyl chloride copolymers used as a base for medical materials, such as vinyl chloride-vinyl acetate copolymers, vinyl chloride-acrylic ester copolymers, and the like.
In the present invention, only 1 kind of the polyvinyl chloride resin may be used, or 2 or more kinds may be used in combination.
(plasticizer)
The plasticizer in the invention has a chemical structural formula shown in a formula (1),
the plasticizer mainly provides good hydrophilicity, biocompatibility and plasticizing performance for matrix polyvinyl chloride resin, and improves the processability of the compounded resin.
In the formula (1), R is selected from-H, or C1-18 straight chain, branched or cyclic alkyl or O ═ CR2-、CH2＝C(CH3)-CH2One of the above-mentioned groups, R is preferably-CH from the viewpoint of plasticization and dissolution resistance3、-CH2CH3、-CH2CH2CH3、-CH2CH2CH2CH3、O＝CR2-one of the above;
r1 can be selected from-CH2-CH2-、-CH2-CH2(CH3)-、-CH2-CH2-CH2-CH2One of the above-mentioned-CH is preferable from the viewpoint of hydrophilicity and plasticization of the plasticizer2-CH2-、-CH2-CH2(CH3) -one of the above.
X is the number of repeating units of the polyoxyalkylene chain, and is selected from 1 to 100, and X is preferably 2 to 80, more preferably 4 to 50, from the viewpoint of plasticization, hydrophilicity and elution resistance.
R2The alkyl group may be selected from a linear, branched or cyclic alkyl group having 4 to 10 carbon atoms, and may be selected from a phenyl group. From the viewpoint of dissolution resistance of the plasticizer, a substituent having a large volume and steric hindrance is selected, and a branched or cyclic alkyl group having 5 to 8 carbon atoms or a phenyl group is preferable, and a cyclic alkyl group or a phenyl group is more preferable.
The above plasticizer compounds are generally synthesized by esterification or transesterification reactions known in the art. From the viewpoint of design flexibility, it is preferable that the plasticizer compound is generally synthesized by an esterification reaction.
When the esterification reaction is used to synthesize the plasticizer compound, the esterification reaction of monoacid and monohydroxy polyether, or the esterification reaction of monoacid and dihydroxy polyether, or the esterification reaction of diacid and monohydroxy polyether can be used.
The monoacid and the diacid used for synthesizing the plasticizer mainly provide large steric hindrance and size of plasticizer molecules, increase the dispersion size in a polyvinyl chloride matrix, improve anchoring efficiency and reduce the migration rate, and the structure of the monoacid comprises but is not limited to alkyl groups with 4-10 carbon atoms in a straight chain, branched chain or cyclic mode, and selectable examples comprise but are not limited to caprylic acid, heptanoic acid, isooctanoic acid, cyclopentanoic acid, isovaleric acid, 4-methylvaleric acid, cyclohexanecarboxylic acid, cycloheptanoic acid, isoheptanoic acid, hexanoic acid, isocaproic acid and benzoic acid. Preference is given to isooctanoic acid and cyclohexanecarboxylic acid. The structure of the dibasic acid includes, but is not limited to, one selected from linear, branched or cyclic alkyl groups having 4 to 10 carbon atoms, and alternative examples include, but are not limited to, succinic acid, glutaric acid, 1, 2-cyclopentanedicarboxylic acid, cyclopentane-1, 3-dicarboxylic acid, adipic acid, phthalic acid, terephthalic acid, isophthalic acid, 1-cyclohexanedicarboxylic acid, 1, 2-cyclohexanedicarboxylic acid, 1, 3-cyclohexanedicarboxylic acid, 1-cyclohexanediacetic acid, and cyclohexanedicarboxylic acid and cyclopentanedicarboxylic acid are preferred from the viewpoint of raw materials already obtained and from the viewpoint of safety.
The monohydroxy polyether may be selected from the group consisting of polyethylene glycol monomethyl ether (MPEG), polyethylene glycol monoethyl ether (PEE), polyethylene glycol monobutyl ether (BPEG), polyethylene glycol monooctyl ether; polypropylene glycol monomethyl ether (MPPG), polypropylene glycol monoethyl ether, polypropylene glycol monobutyl ether (BPPG); the polyethylene glycol monomethyl ether has good water solubility, wettability, lubricity, physiological inertia, no stimulation to human bodies and mild property, and is widely applied to the cosmetic and pharmaceutical industries. The polyethylene glycol monomethyl ether has a large number of flexible ether bonds and terminal hydroxyl groups and has excellent plasticizing performance, the molecular weight of the polyethylene glycol monomethyl ether selected by the invention is 100-2800, preferably 150-2000, and more preferably 250-1500, preferred examples include but are not limited to MPEG-200, MPEG-250, MPEG-300, MPEG-350, MPEG-400, MPEG-450, MPEG-500, MPEG-550, MPEG-600, MPEG-650, MPEG-700, MPEG-750, MPEG-1000, MPEG-2000, and the above MPEG can be used alone or in combination of two or more.
The molecular weight of the polyethylene glycol monoethyl ether selected by the invention is 150-2000, examples include but are not limited to PEE-200, PEE-250, PEE-300, PEE-350, PEE-550 and PEE-750, and from the viewpoint of plasticization, hydrophilicity and migration resistance, 200-1800 is preferred, and 250-1500 is more preferred.
The molecular weight of the polyethylene glycol monobutyl ether selected by the invention is 100-2800, preferably 150-2000, and preferred examples include, but are not limited to, BPEG-350, BPEG-500, BPEG-750 and BPEG-1000.
The molecular weight of the polypropylene glycol monomethyl ether selected by the invention is 150-3000, preferably 200-2000, and the preferred examples include but are not limited to MPPG-200, MPPG-350, MPPG-400, MPPG-600, etc.
The molecular weight of the polypropylene glycol monobutyl ether selected by the invention is 150-3000, preferably 200-2000, and the preferred examples include but are not limited to BPPG-350, BPPG-500, BPPG-750, BPPG-1000 and the like.
Other monohydroxypolyether compounds such as polyoxyethylene polyoxypropylene ether, polyoxyethylene polyoxypropylene pentaerythritol ether, C10-16 fatty alcohol polyoxyethylene polyoxypropylene ether, and methallyl polyoxyethylene ether (APEG) are also included, and optional examples are APEG-700, APEG-800, APEG-900, APEG-1000, APEG-1200, APEG-2000, APEG-2400, APEG-2600, methallyl polyoxyethylene polyoxypropylene ether, and the like.
The bishydroxy polyether may be selected from polyethylene glycol (PEG), polypropylene glycol (PPG), polytetramethylene glycol (PTMG). Among them, examples of the selected polyethylene glycol monomer include, but are not limited to, PEG-200, PEG-300, PEG-400, PEG-600, PEG-800, PEG-1000, PEG-1200, PEG-1500, PEG-2000, PEG-2500, and the molecular weight of the selected polyethylene glycol is 100-2500, preferably 200-2000, more preferably 250-1500, from the viewpoints of plasticization, hydrophilicity and migration resistance.
Examples of selected polypropylene glycol monomers include, without limitation, PPG-200, PPG-400, PPG-600, PPG-1000, PPG-1500, PPG-2000, PPG-3000, PPG-4000; the molecular weight of the polypropylene glycol selected is 150-3000, preferably 200-2000, more preferably 250-1500 from the viewpoint of plasticization, hydrophilicity and migration resistance. Examples of polytetramethylene glycol monomers include, but are not limited to, PTMG-250, PTMG-650, PTMG-1000, PTMG-1400, PTMG-1800, PTMG-2000, PTMG-3000, and the molecular weight of polytetramethylene glycol selected from the viewpoint of plasticization, hydrophilicity and migration resistance is 150-3000, preferably 200-2000, and more preferably 250-1500.
When esterification is employed to synthesize the plasticizer compound, any esterification catalyst known in the art may be used. Examples of the catalyst include: inorganic acids such as concentrated sulfuric acid (>70 wt%), concentrated phosphoric acid (>80 wt%), boric acid, p-toluenesulfonic acid, methanesulfonic acid; inorganic acid ester catalysts such as tetrabutyl titanate, tetrapropyl titanate, tetraisopropyl titanate, isopropyl zirconate, n-propyl zirconate, and the like.
In the present invention, the reaction temperature of the esterification reaction is preferably higher than 100 ℃.
In the esterification reaction, water is formed as a by-product, preferably removed as a vapor during the reaction. For example, by purging with a stream of inert gas (e.g., nitrogen), water trap removal.
In the reaction process, due to different MPEG molecular weights, the viscosity of the system is greatly different, and a certain amount of solvent such as normal hexane and the like can be added according to needs to reduce the viscosity of the system.
After the reaction is completed, unreacted carboxylic acid is removed by distillation under reduced pressure to effect product separation.
Then, the plasticizer compound shown in the structural formula (1) is obtained through neutralization, water washing and other processes as required.
(other compounding agents)
The polyvinyl chloride compounds of the invention may also include, as desired, industrial compounding agents commonly used in polyvinyl chloride processing and use, such as, for example, heat stabilizers, processing aids, secondary plasticizers, lubricants, antioxidants, and the like.
Examples of heat stabilizers selected in the present invention include, without limitation: 1) lead-based stabilizers, selected examples including without limitation tribasic lead salts, dibasic lead salts, and the like, 2) metallic soap stabilizers, selected examples including without limitation zinc stearate, cadmium stearate, calcium stearate, and the like, 3) organotin stabilizers, selected examples including without limitation, for example, dibutyltin dilaurate, dibutyltin dimaleate, methyltin mercaptide, and the like; 4) antimony stabilizers, selected examples include, but are not limited to, antimony mercaptides, antimony carboxylates; 5) organic co-stabilizers, selected examples include without limitation, for example, phosphites, epoxies, polyols, and the like; 6) hydrotalcite-like stabilizers, such as hydrotalcite calcium zinc stabilizers, and the like.
From the viewpoint of medical safety, in order to reduce migration and toxicity of the heat stabilizer, a metal soap stabilizer, an organic auxiliary stabilizer, is preferable; more preferably, the composite stabilizer of calcium stearate and zinc stearate.
Examples of impact modifiers selected in the present invention include, without limitation: chlorinated polyethylene, MBS, ACR, SBS, ABS, EVA, etc.
Examples of secondary plasticizers selected in the present invention include, without limitation: chlorinated paraffin, epoxidized soybean oil, phosphate ester plasticizers, high molecular polyesters and the like, and epoxidized soybean oil and phosphate ester plasticizers are preferred.
The lubricants selected in the present invention are: calcium stearate, chlorinated polyethylene wax, stearic acid, glyceryl stearate, paraffin, polyethylene wax, ammonium stearate,
Examples of antioxidants selected in the present invention include, without limitation: phosphites, such as triphenyl phosphite, diphenylisooctyl phosphite, triisooctyl phosphite, triisodecyl phosphite, trilauryl phosphite, tri- (tridecyl) phosphite; hindered phenols such as 1010,1076,1098,1024, etc.; composite antioxidants such as B225, B900, and B561.
The polyvinyl chloride compound of the present invention may also include other thermoplastic resins other than polyvinyl chloride, as needed, for example, polyolefins such as polyethylene and polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polytetrafluoroethylene, acrylonitrile butadiene styrene resin, acrylic resins, and the like.
The polyvinyl chloride compounds of the invention can be made by methods generally known in the art. For example, the polyvinyl chloride compounds constituting the invention are mixed using standard mixing equipment such as banbury or brabender mixers, extruders, kneaders and two-roll mixers.
The polyvinyl chloride compound of the present invention may be added in any manner, and all the components may be mixed together, or some of the components may be mixed in advance in any combination and batch to obtain a premix, and the remaining components may be mixed in the premix. Further, the respective constituent components may be added together or in portions as needed.
Examples
The present invention will be specifically described with reference to the following examples, but the present invention is not limited to these examples.
< evaluation method >
The polyvinyl chloride compound of the invention is subjected to mechanical property, in vitro cytotoxicity, hemolytic property, light transmittance, plasticizing property, surface hydrophilic property, plasticizer migration and plasticizer volatility test and evaluation.
(mechanical Properties)
Uniformly mixing PVC resin particles with a plasticizer and other auxiliary agents, pre-plasticizing for 2h at 80 ℃, open milling for 10min at 160 ℃, discharging, then hot-pressing for 5min at 180 ℃ and 10MPa, cold-pressing for 5min at 10MPa in a water cooling state, discharging, and standing for 24 h. Samples were cut according to GB/T1040-2006 and tested for tensile strength and elongation at break.
(in vitro cytotoxicity)
In vitro cytotoxicity test: according to ISO10993-5-1999, according to RGB value, the evaluation is carried out by referring to toxicity classification method of United states Pharmacopeia; wherein 0 is non-cytotoxic; 1 is mild cytotoxicity; 2 moderate cytotoxicity; 3 Severe cytotoxicity.
(hemolytic Property)
It is noted that the hemolysis ratio values in GB/T16886.5 and GB/T16886.12 require R < 5%. In the present invention, 2.5% < R < 5% is defined as good, 0.5% < R < 2.5% is defined as excellent, and R < 0.5% is defined as optimal.
(light transmittance)
Samples were prepared in the same manner as in the evaluation of the above-described mechanical properties and measured in accordance with GB/T2410-2008.
(surface hydrophilic Properties)
An OCA-20 water contact angle measuring instrument is adopted to touch 2 microliters of deionized water drops on a sample wafer to be measured, and the contact angle is calculated after 3 seconds.
(plasticizing Property)
The plasticization is evaluated by determining the glass transition temperature of the polyvinyl chloride compound, and the samples are prepared in the same manner as in the evaluation of the mechanical properties described above. Cutting the obtained sample into sample strips with the width of 5mm and the length of 75mm, and testing by using DMTA 2980, wherein the testing mode is a stretching mode, the frequency of the testing condition is 1Hz, and the temperature range is-60-100 ℃.
(migration of plasticizer)
Samples were prepared in the same manner as in the evaluation of mechanical properties described above, and then 3 sets of 5 small pieces each were cut in parallel for each sample piece, weighed and recorded. And (3) respectively soaking the cut 3 groups of sample blocks in ethanol and water at normal temperature for 48h, finally taking out, drying in an oven at 50 ℃ for 24h, and weighing. The percentage of the mass difference before and after soaking (in ethanol or water) of the sample to the mass of the sample before soaking was calculated, and the average of the percentages was defined as the migration rate.
(volatility of plasticizer)
Samples were prepared in the same manner as in the evaluation of the mechanical properties described above, cut and tested according to the ISO176-2005 standard, and bars of the polyvinyl chloride compound were accurately weighed and the weight recorded. The sample strips were placed in a metal container with a suitable amount of activated carbon laid flat on the bottom and were guaranteed not to contact the activated carbon. And (3) placing the metal container in an oven at 100 ℃ for 24 hours, taking out and accurately weighing the mass of the sample strip, and calculating the mass loss.
The following examples are given by way of illustration.
< example 1>
A total of 35g (0.10mol) of MPEG-350, 15.4g (0.12mol) of cyclohexanecarboxylic acid and 1.13g (11.77mmol) of methanesulfonic acid as a catalyst were placed in a 200ml four-necked flask, and a water separator, a stirrer, a nitrogen-introducing tube and a thermometer were attached, respectively. Starting stirring and heating, timing when the temperature reaches 110 ℃, controlling the temperature to keep the system in reflux, and carrying out the whole reaction under the protection of nitrogen. The reaction was stopped after 5 h. After the reaction liquid was cooled, excess carboxylic acid was removed by distillation under reduced pressure, followed by neutralization, washing with water and drying to obtain plasticizer 1.
A polyvinyl chloride homogeneous powder (100phr, S-70, available from Taiwan plastics Co.), plasticizer 1(50phr), and calcium zinc stabilizer (2phr) were mixed uniformly with a high-speed mixer and pre-plasticized at 80 ℃ for 1 hour. To obtain mixed powder. Then, the mixed powder was kneaded at 160 ℃ for 10min with a two-roll kneader, and then, it was taken out and cooled. And putting the prepared cold sheet into a flat vulcanizing instrument with the mould pressing temperature of 180 ℃ and the press gauge pressure of 10MPa, hot-pressing for 5min, taking down the cold sheet, and cold-pressing for 5min in a cold press with the press gauge pressure of 10MPa to obtain a sample sheet. The resulting compound samples were tested for properties and the results are shown in table 1.
< example 2>
A total of 75g (0.10mol) of MPEG-750, 16.6g (0.13mol) of cyclohexanecarboxylic acid, and 1.43g (14.92mmol) of methanesulfonic acid as a catalyst were subjected to the same synthesis procedure as in example 1 to obtain plasticizer 2.
Under the same formulation of polyvinyl chloride compound, the plasticizer 1 in example 1 was replaced with the plasticizer 2, and the sample piece was obtained in the same parts of plasticizer and sample preparation manner as in example 1. The resulting compound samples were tested for properties and the results are shown in table 1.
< example 3>
A total of 150g (0.10mol) of MPEG-1500, 19.2g (0.15mol) of cyclohexanecarboxylic acid, and 1.08g (11.29mmol) of methanesulfonic acid as a catalyst were subjected to the same synthesis procedure as in example 1 to obtain plasticizer 3.
Under the same formulation of polyvinyl chloride compound, the plasticizer 1 in example 1 was replaced with the plasticizer 3, and the sample piece was obtained in the same parts of plasticizer and sample preparation manner as in example 1. The resulting compound samples were tested for properties and the results are shown in table 1.
< example 4>
A polyvinyl chloride homogeneous powder (100phr, S-70 available from Taiwan plastics Co., Ltd.), a plasticizer 2(12phr), and a calcium zinc stabilizer (2phr) were uniformly mixed by a high-speed mixer, and a sample piece was obtained in the same manner as in the preparation of the polyvinyl chloride compound of example 1. The resulting compound samples were tested for properties and the results are shown in table 1.
< example 5>
A polyvinyl chloride homogeneous powder (100phr, S-70 available from Taiwan plastics Co., Ltd.), a plasticizer 2(35phr), and a calcium zinc stabilizer (2phr) were uniformly mixed by a high-speed mixer, and a sample piece was obtained in the same manner as in the preparation of the polyvinyl chloride compound of example 1. The resulting compound samples were tested for properties and the results are shown in table 1.
< example 6>
A total of 35g (0.10mol) of MPEG-350, 10.3g (0.06mol) of 1, 2-cyclohexanedicarboxylic acid and 1.38g (14.42mmol) of methanesulfonic acid as a catalyst were subjected to the same synthesis procedure as in example 1 to obtain plasticizer 4.
Under the same formulation of polyvinyl chloride compound, the plasticizer 1 in example 1 was replaced with the plasticizer 4, and the sample piece was obtained in the same parts of plasticizer and sample preparation manner as in example 1. The resulting compound samples were tested for properties and the results are shown in table 1.
< example 7>
A total of 75g (0.10mol) of MPEG-750, 11.18g (0.065mol) of 1, 2-cyclohexanedicarboxylic acid and 1.36g of concentrated sulfuric acid as a catalyst were subjected to the same synthesis procedure as in example 1 to obtain plasticizer 5.
Under the same formulation of polyvinyl chloride compound, the plasticizer 1 in example 1 was replaced with the plasticizer 5, and a sample piece was obtained in the same parts of plasticizer and sample preparation manner as in example 1. The resulting compound samples were tested for properties and the results are shown in table 1.
< example 8>
A total of 150g (0.10mol) of MPEG-1500, 13.7g (0.08mol) of 1, 2-cyclohexanedicarboxylic acid, and 1.66g of concentrated sulfuric acid as a catalyst were subjected to the same synthesis procedure as in example 1 to obtain plasticizer 6.
Under the same formulation of polyvinyl chloride compound, the plasticizer 1 in example 1 was replaced with the plasticizer 6, and a sample piece was obtained in the same parts of plasticizer and sample preparation manner as in example 1. The resulting compound samples were tested for properties and the results are shown in table 1.
< example 9>
PEG-400+ Cyclohexanecarboxylic acid
A total of 40g (0.1mol) of PEG-400, 30.7g (0.22mol) of cyclohexanecarboxylic acid, and 1.66g of concentrated sulfuric acid as a catalyst were subjected to the same synthesis procedure as in example 1 to obtain plasticizer 7.
Under the same formulation of polyvinyl chloride compound, the plasticizer 1 in example 1 was replaced with the plasticizer 7, and a sample piece was obtained in the same parts of plasticizer and sample preparation manner as in example 1. The resulting compound samples were tested for properties and the results are shown in table 1.
< example 10>
PEG-800+ Cyclohexanecarboxylic acid
A total of 40g (0.05mol) of PEG-800, 16.6g (0.13mol) of cyclohexanecarboxylic acid, and 1.66g of concentrated sulfuric acid as a catalyst were subjected to the same synthesis procedure as in example 1 to obtain plasticizer 8.
Under the same formulation of polyvinyl chloride compound, the plasticizer 1 in example 1 was replaced with the plasticizer 8, and the sample piece was obtained in the same parts of plasticizer and sample preparation manner as in example 1. The resulting compound samples were tested for properties and the results are shown in table 2.
< example 11>
PEG-1500+ Cyclohexanecarboxylic acid
A total of 75g (0.05mol) of PEG-1500, 19.2g (0.15mol) of cyclohexanecarboxylic acid, and 1.66g of concentrated sulfuric acid as a catalyst were subjected to the same synthesis procedure as in example 1 to obtain plasticizer 9.
Under the same formulation of polyvinyl chloride compound, the plasticizer 1 in example 1 was replaced with the plasticizer 9, and a sample piece was obtained in the same parts of plasticizer and sample preparation manner as in example 1. The resulting compound samples were tested for properties and the results are shown in table 2.
< example 12>
MPPG-350+ cyclohexanecarboxylic acid
A total of 35g (0.10mol) of MPPG-350, 15.4g (0.12mol) of cyclohexanecarboxylic acid, and 1.66g of concentrated sulfuric acid as a catalyst were subjected to the same synthesis procedure as in example 1 to obtain plasticizer 10.
Under the same formulation of polyvinyl chloride compound, the plasticizer 1 in example 1 was replaced with the plasticizer 10, and a sample piece was obtained in the same parts of plasticizer and sample preparation manner as in example 1. The resulting compound samples were tested for properties and the results are shown in table 2.
< example 13>
MPPG-600+ Cyclohexanecarboxylic acid
A total of 60g (0.10mol) of MPPG-600, 16.6g (0.13mol) of cyclohexanecarboxylic acid, and 1.66g of concentrated sulfuric acid as a catalyst were subjected to the same synthesis procedure as in example 1 to obtain plasticizer 11.
Under the same formulation of polyvinyl chloride compound, the plasticizer 1 in example 1 was replaced with the plasticizer 11, and a sample piece was obtained in the same parts of plasticizer and sample preparation manner as in example 1. The resulting compound samples were tested for properties and the results are shown in table 1.
< comparative example 1>
A total of 31g (0.5mol) of Ethylene Glycol (EG), 66g (0.51mol) of cyclohexanecarboxylic acid and 1.36g of concentrated sulfuric acid as a catalyst were subjected to the same synthesis procedure as in example 1 to obtain plasticizer D1.
Under the same formulation of polyvinyl chloride compound, plasticizer 1 in example 1 was replaced with plasticizer D1, and a coupon was obtained in the same parts of plasticizer and in the same manner as in example 1. The resulting compound samples were tested for properties and the results are shown in table 2.
< comparative example 2>
PEG3000+ Cyclohexanecarboxylic acid
A total of 100g (0.04mol) of PEG-3000, 12.8g (0.1mol) of cyclohexanecarboxylic acid, and 1.36g of concentrated sulfuric acid as a catalyst were subjected to the same synthesis procedure as in example 1 to obtain plasticizer D2.
Under the same formulation of polyvinyl chloride compound, plasticizer 1 in example 1 was replaced with plasticizer D2, and a coupon was obtained in the same parts of plasticizer and in the same manner as in example 1. The resulting compound samples were tested for properties and the results are shown in table 2.
< comparative example 3>
Using diisononyl cyclohexanedicarboxylate (DINCH), which is a commercially common plasticizer, under the same formulation of the polyvinyl chloride compound, the plasticizer 1 in example 1 was replaced with DINCH, and a sample piece was obtained in the same parts of the plasticizer and the same manner as in example 1. The resulting compound samples were tested for properties and the results are shown in table 2.
< comparative example 4>
Using diisooctyl phthalate (DOP) which is a plasticizer generally used in industry as a plasticizer, the plasticizer 1 in example 1 was replaced with DOP under the same formulation of the polyvinyl chloride compound, and the sample pieces were obtained in the same parts of the plasticizer and the same manner as in example 1. The resulting compound samples were tested for properties and the results are shown in table 2.
TABLE 1
TABLE 2
The above-mentioned embodiments are intended to illustrate the objects, aspects and advantages of the present invention, and it should be understood that the above-mentioned embodiments are only examples of the present invention, and are not intended to limit the present invention, and any modifications, equivalent substitutions, improvements and the like within the spirit and scope of the present invention should be included.
Claims (6)
1. A polyvinyl chloride compound comprises polyvinyl chloride resin and a plasticizer with a structural formula shown as a formula (1), wherein,
in the formula (1), R is selected from-H, or C1-18 straight-chain, branched or cyclic alkyl or O ═ CR2-、CH2＝C(CH3)-CH2-one of the above; r1 can be selected from-CH2-CH2-、-CH2-CH2(CH3)-、-CH2-CH2(CH3) -one of the above; x is selected from 1-100; r2The alkyl group may be selected from a linear, branched or cyclic alkyl group having 4 to 10 carbon atoms, and may be selected from a phenyl group.
2. A polyvinyl chloride compound according to claim 1, characterized in that: in the formula (1), R is selected from-H, or C1-12 straight chain, branched chain or cyclic alkyl, or O ═ CR2-、CH2＝C(CH3)-CH2-one of the above.
3. A polyvinyl chloride compound according to claim 1, characterized in that: in the formula (1), R1 can be selected from-CH2-CH2-、-CH2-CH2(CH3)-、-CH2-CH2-CH2-CH2-one of the above.
4. A polyvinyl chloride compound according to claim 1, characterized in that: in the formula (1), x is selected from 1-100.
5. A polyvinyl chloride compound according to claim 1, characterized in that: in the formula (1), R2The alkyl group may be selected from phenyl groups, and may be selected from linear, branched or cyclic alkyl groups having 4 to 10 carbon atoms.
6. A polyvinyl chloride compound according to claim 1, characterized in that said plasticizer represents 5 to 80 parts by weight per 100 parts by weight of polyvinyl chloride resin.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102186802A (en) * | 2008-09-11 | 2011-09-14 | Sk新技术株式会社 | Novel polyvinyl chloride resin plasticiser |
| CN103328556A (en) * | 2010-11-29 | 2013-09-25 | Sk新技术株式会社 | Plasticizers for resin compositions and resin compositions including the same |
| CN103857735A (en) * | 2011-05-19 | 2014-06-11 | Sk新技术株式会社 | Plasticizers for resin compositions and resin compositions including the same |
| WO2016190354A1 (en) * | 2015-05-27 | 2016-12-01 | 新日本理化株式会社 | Epoxycyclohexane dicarboxylic acid diester, plasticizer, stabilizer and resin composition |
| CN111825786A (en) * | 2019-04-16 | 2020-10-27 | 北京化工大学 | Self-plasticizing vinyl chloride-based copolymer, method of preparing the same, composition including the same, and resin article made from the composition |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102186802A (en) * | 2008-09-11 | 2011-09-14 | Sk新技术株式会社 | Novel polyvinyl chloride resin plasticiser |
| CN103328556A (en) * | 2010-11-29 | 2013-09-25 | Sk新技术株式会社 | Plasticizers for resin compositions and resin compositions including the same |
| CN103857735A (en) * | 2011-05-19 | 2014-06-11 | Sk新技术株式会社 | Plasticizers for resin compositions and resin compositions including the same |
| WO2016190354A1 (en) * | 2015-05-27 | 2016-12-01 | 新日本理化株式会社 | Epoxycyclohexane dicarboxylic acid diester, plasticizer, stabilizer and resin composition |
| CN111825786A (en) * | 2019-04-16 | 2020-10-27 | 北京化工大学 | Self-plasticizing vinyl chloride-based copolymer, method of preparing the same, composition including the same, and resin article made from the composition |
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