CN104558987A - Environment-friendly CPVC (Chlorinated Polyvinyl Chloride) composition with high heat stability - Google Patents
Environment-friendly CPVC (Chlorinated Polyvinyl Chloride) composition with high heat stability Download PDFInfo
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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
- C08L27/22—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 modified by chemical after-treatment
- C08L27/24—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 modified by chemical after-treatment halogenated
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
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- 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
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
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Abstract
The invention discloses an environment-friendly CPVC(Chlorinated Polyvinyl Chloride)composition with high heat stability, belongs to the technical field of plastic processing, and particularly relates to an environment-friendly CPVC composition with high heat stability. The CPVC composition is characterized in that zinc stannate with a hollow molecular sieve structure and a traditional calcium zinc stabilizing agent are used in a united manner as a composite stabilizer. The CPVC composition comprises the following components in parts by weight: 100 parts of a chlorinated polyvinyl chloride resin, wherein the percentage by mass of the chlorinity of the chlorinated polyvinyl chloride resin is 65-68%, 3.0-5.0 parts of a calcium zinc heat stabilizer, 1.0-3.0 parts of the zinc stannate with the hollow molecular sieve structure, 5.0-10.0 parts of an impact modifier, 5.0 parts of a processed flow modified agent, 0.5-1.0 part of an internal lubricating agent, 1.0-1.5 parts of an external lubricating agent, 15 parts of calcium carbonate, and 2.0 parts of titanium dioxide. According to the invention, the initial coloring of products is better restrained, the products can be kept to have higher vicat softening temperature, and the products are environment-friendly and zero-toxic. The size stability of the CPVC composition is good when being heated, and the thermal deformation is small.
Description
Technical field
A kind of environment-friendly type high thermal stability CPVC composition, belongs to technical field of plastic, is specifically related to environment-friendly type high thermal stability CPVC composition.
Background technology
The cl content of CPVC resin is higher, has intensity high, the advantages such as vicat softening temperature is high, acid-alkali-corrosive-resisting, enables to be applied to delivery, the chemical industry fields such as hot acid alkali lye conveying.The thermal stability of CPVC resin is poorer than polyvinyl chloride resin, and the viscosity of resin own is large, and easier dechlorination is decomposed, and polyvinyl chloride resin adds the processing request that the kind of stablizer used in man-hour and consumption are difficult to meet CPVC resin.This just requires that the kind of stablizer used and consumption can provide enough thermal stability to maintain the Continuous maching of CPVC.
CN 101880429A discloses high-tenacity heat-resisting ageing-resisting chlorinated polyvinyl chloride alloy material and preparation method thereof, with lead salt base class thermo-stabilizer, complex lead salt type thermal stabilizing agent, soap type thermal stabilizing agent, rare earth class thermo-stabilizer, one in organic tin thermo-stabilizer, two or more mixture is as thermo-stabilizer, be aided with toughner, processing aid, heat-proof modifier, oxidation inhibitor obtains toughness, resistance toheat, the good CPVC alloy material of ageing-resistant performance, the Vicat softening point of the CPVC alloy material that this invention obtains is 104 ~ 119 DEG C, tensile strength is 45 ~ 64MPa, notched Izod impact strength can improve more than 200%.Lead salt stabilizer can work the mischief to direct labor, user and environment.
CN 1886455A discloses a kind of CPVC composition with good impact strength and thermostability and smooth surface, and with aluminosilicate zeolite, organotin is as stabilising system, and silicone-acrylic analog copolymer is as impact modifier.The Dynamic Thermal steady time (DTS) of obtained CPVC composition is 10 ~ 14min.But organotin can cause composition article vicat softening temperature to decline.
CN 1970616A discloses a kind of method improving chlorinated polyvinyl chloride resin thermostability, adds the mixture of calcium/zinc composite stabilizer and hydrotalcite in the course of processing, to improve the thermostability in CPVC resin treatment process.Although hydrotalcite add the heat-stable time that can extend CPVC resin, the initial coloration of goods can be increased, reduce the whiteness of goods.
From current technical situation, lead salt stabilizer can provide enough stabilising effects for CPVC processing, and the vicat softening temperature of goods is higher simultaneously.But the harm of lead salt stabilizer to environment and human body is apparent.The stabilization efficiency of organotin stabilizer is very high, and the appropriate amount increasing organotin stabilizer can meet the forming process of CPVC, but organotin significantly can reduce the vicat softening temperature of CPVC goods.Therefore, current CPVC industry need badly a kind of environmental protection, stabilising effect good, the little thermo-stabilizer of amplitude is reduced to goods vicat softening temperature.
Summary of the invention
The technical problem to be solved in the present invention is: overcome the deficiencies in the prior art, provides a kind of while raising heat stability of composition energy, keeps goods to have a kind of environment-friendly type high thermal stability of higher vicat softening temperature CPVC composition.
The technical solution adopted for the present invention to solve the technical problems is: this environment-friendly type high thermal stability CPVC composition, it is characterized in that: the weight part of composition consists of the chlorinated polyvinyl chloride resin 100 parts that cl content is 65% ~ 68%, calcium zinc heat stabilizer 3.0 ~ 5.0 parts, the zinc of hollow molecular sieve structure 1.0 ~ 3.0 parts, impact modifier 5.0 ~ 10.0 parts, processing flow ability modifying agent 5.0 parts, internal lubricant 0.5 ~ 1.0 part, external lubricant 1.0 ~ 1.5 parts, 15 parts, calcium carbonate, titanium dioxide 2.0 parts.
Preferably, described chlorinated polyvinyl chloride resin is the chlorinated polyvinyl chloride resin of cl content massfraction 67%.Chlorinated polyvinyl chloride resin is unstable, easily decomposes.The present invention considers the stabilising effect of the one package stabilizer of used calcium zinc stabilizer and zinc, selects the zinc of hollow molecular sieve structure.
Described calcium zinc heat stabilizer is German bear board calcium zinc heat stabilizer R 8965.The present invention's main stabilizer used is zinc, price again due to zinc is higher, for reducing the cost of composition, the present invention adopts the one package stabilizer of calcium zinc stabilizer and zinc, can meet the requirement that CPVC resin is rather harsh to thermostability in the course of processing, goods have higher whiteness and vicat softening temperature.The one package stabilizer of calcium zinc stabilizer and zinc not only reduces cost, also while raising heat stability of composition energy, keeps goods to have higher vicat softening temperature.
Preferably, the zinc of described hollow molecular sieve structure, its inner aperture is at 0.4 ~ 2.0nm, and grain diameter is at 2 ~ 4 μm.The molecular formula of zinc is ZnSnO
3, the particle of zinc has cubic closed packed structure, globosity, octahedral structure, acicular structure, linear structure and hollow molecular sieve structure.Zinc, especially there is hollow molecular sieve structure, and inner aperture is more than or equal to the thermal stability that zinc that 0.4nm and grain diameter be less than or equal to 4 μm effectively can improve CPVC composition, the initial coloration of good suppression goods, and goods can be kept to have higher vicat softening temperature.The zinc-base of zinc can replace the unstable chlorine atom on CPVC molecular chain, stops CPVC dechlorination to form polyene structure and free radical; Stannic acid base can absorb CPVC and decompose the HCl gas produced, thus stops HCl to the catalyzed degradation of CPVC resin.Therefore zinc has the effect of efficient stable CPVC.The zinc of the hollow molecular sieve structure that grain diameter is little due to its specific surface area large, the volumetric concentration of unit weight is large, large with material contact area, more contribute to zinc and replace unstable chlorine atom, the HCl contact reacts produced is decomposed with CPVC, and the zinc of hollow molecular sieve structure can be reacted with the HCl entered in hollow cavity, causes the concentration difference of HCl inside and outside cavity, thus absorbs HCl further.This makes to have hollow molecular sieve structure, and inner aperture is more than or equal to 0.4nm, and it is higher than the zinc stabilization efficiency of common cubic closed packed structure that grain diameter is less than or equal to the zinc of 4 μm.
Impact modifier can use MBS impact modifier, acrylic ester impact-resisting modifier, rubber-like impact modifier in the present invention.
Preferably, described impact-resistant modified be acrylic ester impact-resisting modifier.Acrylic ester impact-resisting modifier is combined more firm with chlorinated polyvinyl chloride resin.The chain length of acrylic ester impact-resisting modifier and the zinc of hollow molecular sieve structure can good combination, form good weather-proof effect.Make the not easily precipitation of acrylic ester impact-resisting modifier, the high thermal stability of CPVC composition is better, uses more environmental protection.
Process flow ability modifying agent in the present invention and can use polymethylmethacrylate, acrylonitritrile-styrene resin, ethylene-vinyl acetate copolymer.
Preferably, described processing flow ability modifying agent is acrylonitritrile-styrene resin.Acrylonitritrile-styrene resin combines more firm as processing flow ability modifying agent chlorinated polyvinyl chloride resin.To the flow modifier better effects if of chlorinated polyvinyl chloride resin, the more effective reduction viscosity of energy, shaping more steady, quality product is more stable.
Internal lubricant can select stearates, pentaerythritol esters, esters of acrylic acid in the present invention.
Preferably, described internal lubricant is calcium stearate.Calcium stearate can more effectively reduce internal friction between chlorinated polyvinyl chloride molecular chain as internal lubricant.Better with the consistency of chlorinated polyvinyl chloride, can evenly spread between its molecular chain, thus reduce the internal friction of molecular chain, improve the mobility of polymkeric substance, improve product surface smooth finish.
External lubricant can select polyethylene wax class, pentaerythritol esters, oxidized polyethlene wax class, montanate class, paraffinic and fatty acid ester in the present invention.
Preferably, described external lubricant is paraffin and polyethylene wax.Paraffin and polyethylene wax more effectively can reduce chlorinated polyvinyl chloride resin interface friction surperficial with forming process machinery in molding process as external lubricant.Play the effect of boundary lubrication, very little with the consistency of polymkeric substance, also can not penetrate in the zinc of hollow molecular sieve structure, affect it and inhale chlorine effect.Be easy to, from the interior shifting of chlorinated polyvinyl chloride resin to surface, form a lubricant molecule layer in interface in the course of processing.And internal cohesive energy is low, the frictional force with equipment surface in moulding process can be reduced, prevent it from attaching to mechanical surface.
Calcium carbonate is optional is in the present invention greater than 1200 object activation treatment calcium carbonate superfine powders.
Preferably, described calcium carbonate is fineness is 2000 orders, through the superfine activated calcium carbonate of 2% titanate coupling agent process.Fineness is 2000 orders, and the superfine activated calcium carbonate through 2% titanate coupling agent process better can adapt to the viscosity of CPVC, in the composition dispersion evenly.
Titanium dioxide can be anatase titanium dioxide and Rutile type Titanium Dioxide in the present invention.
Preferably, described titanium dioxide is Rutile type Titanium Dioxide.The viscosity better adaptability of Rutile type Titanium Dioxide and chlorinated polyvinyl chloride resin, dispersion evenly.Can more effectively improve its thermotolerance, photostabilization, weathering resistance, physical and chemical performance is better improved, strengthen the physical strength of goods, increase the service life.
Taken by a certain percentage by above-mentioned material and mix in high-speed mixer, rotating speed is 700 ~ 1400 turns, mixes 8 ~ 10 minutes blowings, and cooling is high thermal stability CPVC composition.
The CPVC high thermal stability composition that the present composition is made up of CPVC resin, calcium zinc heat stabilizer, zinc, lubricant, processing flow ability modifying agent, toughner, filler and titanium dioxide.CPVC due to viscosity large, easily decompose, comparatively polyvinyl chloride resin is more difficult to make forming process.Although the thiol organotin type of liquid stabiliser that current stabilization efficiency is higher can by increasing addition to reach good processing thermostable effect, it is too large to the reduction of goods vicat softening temperature.The stabilization efficiency of calcium zinc stabilizer is on the low side, and a large amount of interpolations of composite portion low melting point lubricant also can cause the reduction of goods vicat softening temperature usually.
Compared with prior art, the beneficial effect that a kind of environment-friendly type high thermal stability CPVC composition of the present invention has is: the present invention uses zinc as stablizer, especially there is hollow molecular sieve structure, inner aperture is more than or equal to the thermal stability that zinc that 0.4nm and grain diameter be less than or equal to 4 μm effectively can improve CPVC composition, the initial coloration of good suppression goods, goods can be kept to have higher vicat softening temperature, and environment-protecting asepsis.Can not direct labor, user and environment work the mischief in preparation process.Higher vicat softening temperature ensure that the environment for use of CPVC composition, and vicat softening temperature is higher, and dimensional stability when CPVC composition is heated is better, and thermal distortion is less, and namely heat-resistant deforming ability is better, and rigidity is larger, and modulus is higher, ensures use safety.
Embodiment
Below by specific embodiment, a kind of environment-friendly type high thermal stability of the present invention CPVC composition is described further, wherein considers production cost and high heat stability effect example 2 is most preferred embodiment.
The embodiment proportioning component of this environment-friendly type high thermal stability CPVC composition is as shown in table 1.
Table 1 embodiment 1 ~ 8 high thermal stability CPVC composite formula component (with parts by weight)
Wherein embodiment 1 ~ 5 is super-fine active calcium carbides be fineness is 2000 orders, through the superfine activated calcium carbonate of 2% titanate coupling agent process.Cl content in embodiment 1 ~ 5 in CPVC is the chlorinated polyvinyl chloride resin of cl content massfraction 67%, and embodiment 7 is the chlorinated polyvinyl chloride resin of cl content massfraction 66%, and embodiment 8 is the chlorinated polyvinyl chloride resin of cl content massfraction 68%.In each embodiment, zinc used is the zinc of hollow molecular sieve structure, and its inner aperture is at 0.4 ~ 2.0nm, and grain diameter is at 2 ~ 4 μm.
Comparative example 1 ~ 5
Comparative example 1 ~ 5 is for comparing the comparative formula of the properties design of high thermal stability CPVC composition of the present invention.The component proportion of comparative formula is as shown in table 2.
The recipe ingredient (with parts by weight) of table 2 comparative example 1 ~ 5
Embodiment and each component of comparative example are put into high-speed mixer mixing rotating speed 700 ~ 1400r/min by formula rate, to 110 DEG C, is discharged in low-speed mixer and is cooled to 30 ~ 40 DEG C, blowing is high heat stability CPVC and expects.The material mixed is opened in 180 DEG C of two roller mills and is smelt sheet, at extrusion press 190 DEG C, suppress 4mm sheet material, test sample whiteness, impact property and vicat softening temperature.Dynamic Thermal stability test utilizes Brabendar to plastify instrument test, and test condition is 200 DEG C, 60 revs/min.Simple beam impact strength is tested according to according to standard GB/T/T 1043-2008, A type breach.Vicat softening temperature is according to standard GB/T/T 1633-2000, B
50method is tested.Detected result is as shown in table 3.
Table 3 high thermal stability CPVC composition properties detected result
Can be found out by embodiment 1 ~ 5, zinc can effectively improve CPVC composition dynamic thermal stability can and goods whiteness, and along with the raising of zinc content, the vicat softening temperature of goods increases.Comparative example 1 ~ 3 shows, the dynamic stability performance and the goods whiteness that are used alone calcium zinc stabilizer are not so good as the good of calcium zinc stabilizer/zinc one package stabilizer, and along with the increase of calcium zinc stabilizer amount, the vicat softening temperature of goods slightly reduces.Comparative example 4,5 shows, organotin add the vicat softening temperature that obviously can reduce composition.
The above is only preferred embodiment of the present invention, and be not restriction the present invention being made to other form, any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be modified as the Equivalent embodiments of equivalent variations.But everyly do not depart from technical solution of the present invention content, any simple modification, equivalent variations and the remodeling done above embodiment according to technical spirit of the present invention, still belong to the protection domain of technical solution of the present invention.
Claims (9)
1. an environment-friendly type high thermal stability CPVC composition, it is characterized in that: the weight part of composition consists of the chlorinated polyvinyl chloride resin 100 parts of cl content massfraction 65% ~ 68%, calcium zinc heat stabilizer 3.0 ~ 5.0 parts, the zinc of hollow molecular sieve structure 1.0 ~ 3.0 parts, impact modifier 5.0 ~ 10.0 parts, processing flow ability modifying agent 5.0 parts, internal lubricant 0.5 ~ 1.0 part, external lubricant 1.0 ~ 1.5 parts, 15 parts, calcium carbonate, titanium dioxide 2.0 parts.
2. a kind of environment-friendly type high thermal stability CPVC composition according to claim 1, is characterized in that: described chlorinated polyvinyl chloride resin is the chlorinated polyvinyl chloride resin of cl content massfraction 67%.
3. a kind of environment-friendly type high thermal stability CPVC composition according to claim 1, it is characterized in that: the zinc of described hollow molecular sieve structure, its inner aperture is at 0.4 ~ 2.0nm, and grain diameter is at 2 ~ 4 μm.
4. a kind of environment-friendly type high thermal stability CPVC composition according to claim 1, is characterized in that: described impact modifier is acrylic ester impact-resisting modifier.
5. a kind of environment-friendly type high thermal stability CPVC composition according to claim 1, is characterized in that: described processing flow ability modifying agent is acrylonitritrile-styrene resin.
6. a kind of environment-friendly type high thermal stability CPVC composition according to claim 1, is characterized in that: described internal lubricant is calcium stearate.
7. a kind of environment-friendly type high thermal stability CPVC composition according to claim 1, is characterized in that: described external lubricant is paraffin and polyethylene wax.
8. a kind of environment-friendly type high thermal stability CPVC composition according to claim 1, is characterized in that: described calcium carbonate is fineness is 2000 orders, through the superfine activated calcium carbonate of 2% titanate coupling agent process.
9. a kind of environment-friendly type high thermal stability CPVC composition according to claim 1, is characterized in that: described titanium dioxide is Rutile type Titanium Dioxide.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104927261A (en) * | 2015-05-21 | 2015-09-23 | 青岛科凯达橡塑有限公司 | Corrosion-resistant electric conduction and heat conduction chlorinated polyvinyl chloride resin material and preparation method and application thereof |
| CN107177147A (en) * | 2017-06-05 | 2017-09-19 | 潍坊高信新材料有限公司 | A kind of higher-dimension card, corrosion-resistant, high intensity CPVC sheet materials and preparation method thereof |
| CN109651737A (en) * | 2018-12-05 | 2019-04-19 | 上海氯碱化工股份有限公司 | Chliorinated polyvinyl chloride elastic material and its preparation method and application |
| CN112321977A (en) * | 2020-10-12 | 2021-02-05 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | Preparation method of CPVC (chlorinated polyvinyl chloride) composition with high thermal stability |
| CN113603988A (en) * | 2021-08-27 | 2021-11-05 | 山东高信化学股份有限公司 | High-flame-retardant CPVC (chlorinated polyvinyl chloride) automotive plate composition and preparation method thereof |
| CN114350090A (en) * | 2022-01-20 | 2022-04-15 | 济南新材料产业技术研究院 | High-temperature-resistant polymer alloy bridge and preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101880429A (en) * | 2010-08-11 | 2010-11-10 | 聊城大学 | High-tenacity heat-resisting ageing-resisting chlorinated polyvinyl chloride alloy material and preparation method thereof |
| CN102477196B (en) * | 2010-11-30 | 2014-01-29 | 山东慧科助剂股份有限公司 | Novel molecular sieve PVC composite stabilizing agent and its preparation method |
-
2013
- 2013-10-22 CN CN201310497031.8A patent/CN104558987B/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104927261A (en) * | 2015-05-21 | 2015-09-23 | 青岛科凯达橡塑有限公司 | Corrosion-resistant electric conduction and heat conduction chlorinated polyvinyl chloride resin material and preparation method and application thereof |
| CN107177147A (en) * | 2017-06-05 | 2017-09-19 | 潍坊高信新材料有限公司 | A kind of higher-dimension card, corrosion-resistant, high intensity CPVC sheet materials and preparation method thereof |
| CN109651737A (en) * | 2018-12-05 | 2019-04-19 | 上海氯碱化工股份有限公司 | Chliorinated polyvinyl chloride elastic material and its preparation method and application |
| CN112321977A (en) * | 2020-10-12 | 2021-02-05 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | Preparation method of CPVC (chlorinated polyvinyl chloride) composition with high thermal stability |
| CN113603988A (en) * | 2021-08-27 | 2021-11-05 | 山东高信化学股份有限公司 | High-flame-retardant CPVC (chlorinated polyvinyl chloride) automotive plate composition and preparation method thereof |
| CN114350090A (en) * | 2022-01-20 | 2022-04-15 | 济南新材料产业技术研究院 | High-temperature-resistant polymer alloy bridge and preparation method and application thereof |
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