CN108504001A - A kind of modified calcium carbonate filled PVC tubing and preparation method thereof - Google Patents
A kind of modified calcium carbonate filled PVC tubing and preparation method thereof Download PDFInfo
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- CN108504001A CN108504001A CN201810714664.2A CN201810714664A CN108504001A CN 108504001 A CN108504001 A CN 108504001A CN 201810714664 A CN201810714664 A CN 201810714664A CN 108504001 A CN108504001 A CN 108504001A
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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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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L57/00—Protection of pipes or objects of similar shape against external or internal damage or wear
- F16L57/02—Protection of pipes or objects of similar shape against external or internal damage or wear against cracking or buckling
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L57/00—Protection of pipes or objects of similar shape against external or internal damage or wear
- F16L57/04—Protection of pipes or objects of similar shape against external or internal damage or wear against fire or other external sources of extreme heat
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L57/00—Protection of pipes or objects of similar shape against external or internal damage or wear
- F16L57/06—Protection of pipes or objects of similar shape against external or internal damage or wear against wear
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L58/00—Protection of pipes or pipe fittings against corrosion or incrustation
- F16L58/02—Protection of pipes or pipe fittings against corrosion or incrustation by means of internal or external coatings
- F16L58/04—Coatings characterised by the materials used
- F16L58/10—Coatings characterised by the materials used by rubber or plastics
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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
- C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
- C08K2003/2213—Oxides; Hydroxides of metals of rare earth metal of cerium
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- 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
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C08L2201/02—Flame or fire retardant/resistant
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- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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- 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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Abstract
The invention discloses a kind of modified calcium carbonate filled PVC tubing and preparation method thereof, the PVC pipe includes the raw material of following parts by weight：35 parts of 100 parts of polyvinyl chloride resin, 5 10 parts of bismaleimide, 35 parts of acrylic acid copolymer-maleic anhydride, 13 parts of poly- aminopropyltriethoxy silsesquioxane, 12 parts of maleic acid castor oil ester, 15 30 parts of modified nano calcium carbonate, 35 parts of asbestos fibre, 13 parts of coupling agent, 0.5 2 parts of crosslinking agent, 0.5 1.5 parts of antioxidant, 0.5 1.5 parts of stabilizer, 12 parts of antiseptic and processing aid.PVC pipe provided by the invention due to the coordinative role of unique composition of raw materials and each component have many advantages, such as high intensity, high tenacity, shock resistance are strong, heat-resisting, bacteriostasis antibiosis is strong, it is ageing-resistant, be unlikely to deform, stability is good, ageing-resistant, its processing technology is simple, cost is more cheap, wide market.
Description
Technical field
The present invention relates to plastic pipe technical field, specifically a kind of modified calcium carbonate filled PVC tubing and its preparation side
Method.
Background technology
PVC tubing has the characteristics that corrosion resistance is strong, intensity is high, rigidity is good, therefore, be widely used in building water supply and drainage,
The construction industries such as town and country plumbing, city gas, electric power and cable jacket, industrial fluids conveying, agricultural irrigation, municipal administration, industry and
Agriculture field is the plastic pipe that a kind of scope of application is only second to polyethylene.But due to polyvinyl chloride resin itself there are poor heat resistance,
Impact resistance difference problem, so as to cause the plastic pipe prepared with polyvinyl chloride resin, accordingly there is also poor heat resistances, in illumination item
It is easy to aging under part, deformation, it is brittle the problems such as, shorten the service life of tubing.
Nano-calcium carbonate is the new type functional nano-sized filler of function admirable particularly important in technical calcium carbonate, it is not
It is only capable of playing the role of filling increase-volume, reduces cost, can more improve the surface color degree of filled articles, improve the resultant force of product
Performance is learned, the fields such as plastics, rubber, coating, adhesive, ink are widely used in.Nano-calcium carbonate is as PVC plastic pipe
One of important filler, but since Nano particles of calcium carbonate grain size is smaller, the atomicity on surface is more, then surface energy is higher, inhales
Attached effect is stronger, mutually reunites between each particle.As a kind of inorganic filler, particle surface is hydrophilic to be dredged followed by nano-calcium carbonate
Oil, with the compatibility of polyvinyl chloride resin it is poor, easily form aggregation, cause high polymer internal flaw, mechanical property be deteriorated.In order to improve
The filling capacity of nano-calcium carbonate, it is necessary to which rational table is carried out to nano-calcium carbonate using effective technique and surface modifying method
Face is modified.
It is usually at present aliphatic acid or its salt to the surface conditioning agent in nono calcium carbonate modified method, mainly selected,
Although the dispersibility and processing fluidity of system make moderate progress, since polyvinyl chloride resin is difficult effectively to be tied with nano-calcium carbonate filler
It closes, leads to the interfacial adhesion force difference of matrix and filler, to cause the mechanical strength of PVC pipe not high.Secondly existing pvc pipe
Material there is also poor heat resistance, impact resistance are poor, easy to aging under illumination condition, deformation, it is brittle the problems such as, shorten tubing
Service life.
Invention content
Present invention aims at offer one kind with high intensity, high tenacity, corrosion-resistant, heat-resist, impact resistance is strong, resistance
The PVC pipe and preparation method thereof for the advantages that combustion property is good, bacteriostasis antibiosis is strong.
In order to achieve the goal above, the technical solution adopted by the present invention is as follows：
A kind of modified calcium carbonate filled PVC tubing, the PVC pipe include the raw material of following parts by weight：100 parts of polyvinyl chloride resin,
5-10 parts of bismaleimide, 3-5 parts of acrylic acid-maleic anhydride copolymer, 1-3 parts of poly- aminopropyltriethoxy silsesquioxane, horse
Sour castor oil ester 1-2 parts next, 15-30 parts of modified nano calcium carbonate, 3-5 parts of asbestos fibre, 1-3 parts of coupling agent, crosslinking agent 0.5-2
Part, 0.5-1.5 parts of antioxidant, 0.5-1.5 parts of stabilizer, 1-2 parts of antiseptic and 3-5 parts of processing aid.
As currently preferred technical solution：The preparation of the modified calcium carbonate includes the following steps：
（1）Digestion reactor is added in quick lime and hot water and carries out digestion reaction, removal of impurities is still aging, and dilution obtains milk of lime
Liquid；
（2）Lime slurry is delivered to carbonation reaction tower, carbon dioxide is passed through and carries out carburizing reagent, be added in carbonisation
Chemical additives and dispersant, carbonization to pH value are 6.5-7.5, and stopping is passed through carbon dioxide, and controls the specific surface of calcium carbonate
Product is 30-50m2/ g obtains nano-calcium carbonate slurry；The chemical additives are made of phytic acid and tartaric acid, and addition is carbon
The 0.5-1.5% of sour calcium dry weight；The dispersant is by polyoxyethylene glycerol ether monostearate and the sulfonated hydrogen of succinate
Change castor oil composition, addition is the 1.5-3% of calcium carbonate dry weight；
（3）Nano-calcium carbonate slurry is delivered to ultrasonic stirrer, and is heated to 60-80 DEG C, is added by oleic acid diethanol
The addition of the surface conditioning agent of amide borate and octaphenyl cagelike silsesquioxane composition, surface conditioning agent is calcium carbonate dry
The 1.5-3% of base weight amount is stirred by ultrasonic 30-60min, obtains modified nano calcium carbonate slurry；
（4）Modified nano calcium carbonate slurry dry, pulverize to get modified nano calcium carbonate again.
As currently preferred technical solution：The mass ratio of phytic acid and tartaric acid is 1 in the chemical additives:1-3.
As currently preferred technical solution：The dispersant is 1-2 by mass ratio:1 polyoxyethylene glycerol ether list
Stearate and the sulfonated rilanit special composition of succinate.
As currently preferred technical solution：Oleic diethanola mide borate ester and octaphenyl in the surface conditioning agent
The mass ratio of cagelike silsesquioxane is 1-2:1.
As currently preferred technical solution：The coupling agent is coupled by aluminium methacrylate-zirconium coupling agent and rare earth
Agent forms.
As currently preferred technical solution：The crosslinking agent is by starch sulfonic group succinate and polyacrylamide group
At.
As currently preferred technical solution：The antiseptic is made of chitosan and ceria.
As currently preferred technical solution：The processing aid is by ricinoleic acid butyl ester sodium sulphate and poly- aminopropyl first
Base silsesquioxane forms.
The preparation method of modified calcium carbonate filled PVC tubing of the present invention, includes the following steps：
S1:Each raw material is weighed according to aforementioned proportion, polyvinyl chloride resin, bismaleimide, acrylic acid-maleic anhydride copolymer are added
Enter blender, is heated to 60-80 DEG C and stirs evenly, obtain hybrid resin；
S2:80-100 DEG C is heated in hybrid resin, be added poly- aminopropyltriethoxy silsesquioxane, maleic acid castor oil ester and
Asbestos fibre is uniformly mixed, adds coupling agent, crosslinking agent, antioxidant, stabilizer, antiseptic and processing aid, fully mixed
It closes uniformly, obtains tubing base-material；
S3:Aforementioned tubes base-material is delivered to double screw extruder, extrusion forming at being 180-200 DEG C in temperature, cooling and shaping,
Up to PVC pipe.
Compared with prior art, it advantages of the present invention and has the beneficial effect that：
1, PVC pipe provided by the invention is since the coordinative role of unique composition of raw materials and each component is with high intensity, high-ductility
Property, shock resistance is strong, heat-resisting, bacteriostasis antibiosis is strong, it is ageing-resistant, be unlikely to deform, the advantages that stability is good, ageing-resistant, add
Work is simple for process, cost is more cheap, wide market.
2, nano-calcium carbonate used in PVC pipe of the present invention is added in carbonation is made of phytic acid and tartaric acid
Chemical additives can be very good control calcium carbonate crystallite dimension and stability, since the special construction of phytic acid can also improve
The mechanical property of calcium carbonate and compatibility with other components.
3, the present invention is added during calcium carbonate reaction by polyoxyethylene glycerol ether monostearate and succinate sulphur
It is acidified the dispersant of rilanit special composition, the dispersibility of reaction system is improved, agglomerated calcium carbonate particle can be effectively prevent
It generates, further uses oleic diethanola mide borate ester and octaphenyl cagelike silsesquioxane to carry out surface modification, due to two
Person is inorganic-organic hybridization structure, introduces the groups such as silicon oxygen bond, amide, carboxyl, boric acid, phenyl on calcium carbonate particle surface, no
The dispersibility of calcium carbonate and the compatibility with polyvinyl chloride resin can be only improved, due to each group and PVC pipe System forming network knot
Structure improves PVC pipe reaction system interfacial adhesion so that it is tough that calcium carbonate achievees the effect that enhancing is mended, moreover it is possible to improve PVC pipe
Notch impact strength, tensile break strength, heat resistance, anti-flammability and anti-aging property.
4, in the formula of PVC pipe of the present invention using polyvinyl chloride resin as primary raw material, then be equipped with bismaleimide, third
Olefin(e) acid-copolymer-maleic anhydride improves toughness, impact resistance, heat resistance and the inoxidizability of tubing system, effectively overcomes
The defects of polyvinyl chloride resin itself is brittle, thermo-labile.
5,1-3 parts of poly- aminopropyltriethoxy silsesquioxane, maleic acid castor oil is added in the present invention in PVC pipe formula
Ester, can be improved the dispersibility of the compatibility and each component between inorganic-organic raw material, and used coupling agent is a kind of with hydroxyl
The organic matter of the various actives group such as base, carboxyl, carbonyl, itself can form network structure, and the active group in network structure can
With the effect of resin, dual-network structure is formed, the degree of cross linking and reinforcement are improved；Used processing aid is remarkably improved whole
The dispersibility and processing performance of a reaction system, improve the finish of product, moreover it is possible to improve the heat resistance and toughening effect of product.
6, the present invention is using chitosan and ceria as antiseptic, to Escherichia coli, Huang under room temperature or high-temperature condition
Golden staphylococci, fungi etc. have significant antibacterial and fungistatic effect, and chitosan can also improve the inoxidizability of tubing.
7, crosslinking agent used in the present invention not only makes entire reaction system form network structure, improves the intensity of tubing
And toughness, moreover it is possible to improve the heat resistance and antioxidant of tubing.
Specific implementation mode
Technical scheme of the present invention is further described below in conjunction with specific embodiment, but is not limited to the present invention's
Protection domain.
Embodiment 1
A kind of modified calcium carbonate filled PVC tubing, includes the raw material of following parts by weight：100 parts of polyvinyl chloride resin, bismaleimide
8 parts of amine, 3 parts of acrylic acid-maleic anhydride copolymer, 2.5 parts of poly- aminopropyltriethoxy silsesquioxane, maleic acid castor oil ester 1.5
It is part, 25 parts of modified nano calcium carbonate, 4 parts of asbestos fibre, 2.5 parts of coupling agent, 1 part of crosslinking agent, 1 part of 1010 antioxidant, organic
4 parts of 1.2 parts of tin stabilizer, 1.5 parts of antiseptic and processing aid.
The preparation of the modified calcium carbonate includes the following steps：
（1）According to mass ratio it is 1 by quick lime and 60 DEG C of hot water:5, which are added digestion reactor, carries out digestion reaction, cleans, stands
It is aged 48h, it is 1.060 to be diluted to proportion, obtains lime slurry；
（2）Lime slurry is delivered to carbonation reaction tower, carbon dioxide is passed through and carries out carburizing reagent, be added in carbonisation
Chemical additives and dispersant, carbonization to pH value are 7, and stopping is passed through carbon dioxide, and the specific surface area for controlling calcium carbonate is
38.6m2/ g obtains nano-calcium carbonate slurry；The chemical additives are 1 by mass ratio:2 phytic acid and tartaric acid composition, adds
Enter 0.9% that amount is calcium carbonate dry weight；The dispersant is 1 by mass ratio:1 polyoxyethylene glycerol ether monostearate
With the sulfonated rilanit special composition of succinate, addition is the 2% of calcium carbonate dry weight；
（3）Nano-calcium carbonate slurry is delivered to ultrasonic stirrer, and is heated to 70 DEG C, it is 2 to add by mass ratio:1 oil
The surface conditioning agent of sour diglycollic amide borate and octaphenyl cagelike silsesquioxane composition, the addition of surface conditioning agent are
The 2.4% of calcium carbonate dry weight is stirred by ultrasonic 45min, obtains modified nano calcium carbonate slurry；
（4）Modified nano calcium carbonate slurry dry, pulverize to get modified nano calcium carbonate again.
The coupling agent is 2 by mass ratio:1 aluminium methacrylate-zirconium coupling agent and rare-earth coupling agent composition.The friendship
It is 1 to join agent by mass ratio:1 starch sulfonic group succinate and polyacrylamide composition.The antiseptic is by chitosan and two
Cerium oxide forms.The processing aid is 3 by mass ratio:1 ricinoleic acid butyl ester sodium sulphate and poly- aminopropyltriethoxy sesquialter silicon
Oxygen alkane forms.
The preparation method of the modified calcium carbonate filled PVC tubing, includes the following steps：
S1:Each raw material is weighed according to aforementioned proportion, polyvinyl chloride resin, bismaleimide, acrylic acid-maleic anhydride copolymer are added
Enter blender, is heated to 75 DEG C and stirs evenly, obtain hybrid resin；
S2:It is heated to 90 DEG C in hybrid resin, poly- aminopropyltriethoxy silsesquioxane, maleic acid castor oil ester and asbestos are added
Fiber is uniformly mixed, adds coupling agent, crosslinking agent, antioxidant, stabilizer, antiseptic and processing aid, is sufficiently mixed
It is even, obtain tubing base-material；
S3:Aforementioned tubes base-material is delivered to double screw extruder, extrusion forming at being 180-200 DEG C in temperature, cooling and shaping,
Up to PVC pipe.
Embodiment 2
A kind of modified calcium carbonate filled PVC tubing, includes the raw material of following parts by weight：100 parts of polyvinyl chloride resin, bismaleimide
6 parts of amine, 4 parts of acrylic acid-maleic anhydride copolymer, 1.5 parts of poly- aminopropyltriethoxy silsesquioxane, 1 part of maleic acid castor oil ester,
20 parts of modified nano calcium carbonate, 3 parts of asbestos fibre, 1 part of coupling agent, 1.5 parts of crosslinking agent, 1.5 parts of 1076 antioxidant, organotin
3.5 parts of 0.8 part of stabilizer, 2 parts of antiseptic and processing aid.
The preparation of the modified calcium carbonate includes the following steps：
（1）According to mass ratio it is 1 by quick lime and 70 DEG C of hot water:4, which are added digestion reactor, carries out digestion reaction, cleans, stands
It is aged 36h, it is 1.065 to be diluted to proportion, obtains lime slurry；
（2）Lime slurry is delivered to carbonation reaction tower, carbon dioxide is passed through and carries out carburizing reagent, be added in carbonisation
Chemical additives and dispersant, carbonization to pH value are 6.5, and stopping is passed through carbon dioxide, and the specific surface area for controlling calcium carbonate is
42.9m2/ g obtains nano-calcium carbonate slurry；The chemical additives are 1 by mass ratio:3 phytic acid and tartaric acid composition, adds
Enter 1.2% that amount is calcium carbonate dry weight；The dispersant is 2 by mass ratio:1 polyoxyethylene glycerol ether monostearate
With the sulfonated rilanit special composition of succinate, addition is the 3% of calcium carbonate dry weight；
（3）Nano-calcium carbonate slurry is delivered to ultrasonic stirrer, and is heated to 80 DEG C, it is 1 to add by mass ratio:1 oil
The surface conditioning agent of sour diglycollic amide borate and octaphenyl cagelike silsesquioxane composition, the addition of surface conditioning agent are
The 1.8% of calcium carbonate dry weight is stirred by ultrasonic 60min, obtains modified nano calcium carbonate slurry；
（4）Modified nano calcium carbonate slurry dry, pulverize to get modified nano calcium carbonate again.
The coupling agent is 1 by mass ratio:1 aluminium methacrylate-zirconium coupling agent and rare-earth coupling agent composition.The friendship
It is 3 to join agent by mass ratio:1 starch sulfonic group succinate and polyacrylamide composition.The antiseptic is by chitosan and two
Cerium oxide forms.The processing aid is 2 by mass ratio:1 ricinoleic acid butyl ester sodium sulphate and poly- aminopropyltriethoxy sesquialter silicon
Oxygen alkane forms.
The preparation method of the modified calcium carbonate filled PVC tubing, includes the following steps：
S1:Each raw material is weighed according to aforementioned proportion, polyvinyl chloride resin, bismaleimide, acrylic acid-maleic anhydride copolymer are added
Enter blender, is heated to 65 DEG C and stirs evenly, obtain hybrid resin；
S2:It is heated to 100 DEG C in hybrid resin, poly- aminopropyltriethoxy silsesquioxane, maleic acid castor oil ester and stone is added
Cotton fiber is uniformly mixed, adds coupling agent, crosslinking agent, antioxidant, stabilizer, antiseptic and processing aid, be sufficiently mixed
Uniformly, tubing base-material is obtained；
S3:Aforementioned tubes base-material is delivered to double screw extruder, extrusion forming at being 180-200 DEG C in temperature, cooling and shaping,
Up to PVC pipe.
Embodiment 3
A kind of modified calcium carbonate filled PVC tubing, includes the raw material of following parts by weight：100 parts of polyvinyl chloride resin, bismaleimide
7 parts of amine, 5 parts of acrylic acid-maleic anhydride copolymer, 3 parts of poly- aminopropyltriethoxy silsesquioxane, 1.5 parts of maleic acid castor oil ester,
30 parts of modified nano calcium carbonate, 4 parts of asbestos fibre, 2.5 parts of coupling agent, 1.2 parts of crosslinking agent, 0.8 part of 1010 antioxidant, calcium zinc
5 parts of 1.2 parts of stabilizer, 1 part of antiseptic and processing aid.
The preparation of the modified calcium carbonate includes the following steps：
（1）According to mass ratio it is 1 by quick lime and 60 DEG C of hot water:6, which are added digestion reactor, carries out digestion reaction, cleans, stands
It is aged 30h, it is 1.070 to be diluted to proportion, obtains lime slurry；
（2）Lime slurry is delivered to carbonation reaction tower, carbon dioxide is passed through and carries out carburizing reagent, be added in carbonisation
Chemical additives and dispersant, carbonization to pH value are 7, and stopping is passed through carbon dioxide, and the specific surface area for controlling calcium carbonate is
32.8m2/ g obtains nano-calcium carbonate slurry；The chemical additives are 1 by mass ratio:1 phytic acid and tartaric acid composition, adds
Enter 0.5% that amount is calcium carbonate dry weight；The dispersant is 1 by mass ratio:1 polyoxyethylene glycerol ether monostearate
With the sulfonated rilanit special composition of succinate, addition is the 2% of calcium carbonate dry weight；
（3）Nano-calcium carbonate slurry is delivered to ultrasonic stirrer, and is heated to 70 DEG C, it is 2 to add by mass ratio:1 oil
The surface conditioning agent of sour diglycollic amide borate and octaphenyl cagelike silsesquioxane composition, the addition of surface conditioning agent are
The 2.7% of calcium carbonate dry weight is stirred by ultrasonic 30min, obtains modified nano calcium carbonate slurry；
（4）Modified nano calcium carbonate slurry dry, pulverize to get modified nano calcium carbonate again.
The coupling agent is 1.5 by mass ratio:1 aluminium methacrylate-zirconium coupling agent and rare-earth coupling agent composition.It is described
Crosslinking agent is 2 by mass ratio:1 starch sulfonic group succinate and polyacrylamide composition.The antiseptic by chitosan and
Ceria forms.The processing aid is 1 by mass ratio:1 ricinoleic acid butyl ester sodium sulphate and poly- aminopropyltriethoxy sesquialter
Siloxanes forms.
The preparation method of the modified calcium carbonate filled PVC tubing, includes the following steps：
S1:Each raw material is weighed according to aforementioned proportion, polyvinyl chloride resin, bismaleimide, acrylic acid-maleic anhydride copolymer are added
Enter blender, is heated to 70 DEG C and stirs evenly, obtain hybrid resin；
S2:It is heated to 80 DEG C in hybrid resin, poly- aminopropyltriethoxy silsesquioxane, maleic acid castor oil ester and asbestos are added
Fiber is uniformly mixed, adds coupling agent, crosslinking agent, antioxidant, stabilizer, antiseptic and processing aid, is sufficiently mixed
It is even, obtain tubing base-material；
S3:Aforementioned tubes base-material is delivered to double screw extruder, extrusion forming at being 180-200 DEG C in temperature, cooling and shaping,
Up to PVC pipe.
Embodiment 4
A kind of modified calcium carbonate filled PVC tubing, includes the raw material of following parts by weight：100 parts of polyvinyl chloride resin, bismaleimide
5 parts of amine, 2 parts of poly- aminopropyltriethoxy silsesquioxane, 1 part of maleic acid castor oil ester, changes 4 parts of acrylic acid-maleic anhydride copolymer
25 parts of nano-calcium carbonate of property, 5 parts of asbestos fibre, 1.5 parts of coupling agent, 1.2 parts of crosslinking agent, 1 part of CA antioxidants, calcium zinc stabilizer
3 parts of 0.8 part, 1.5 parts of antiseptic and processing aid.
The preparation of the modified calcium carbonate includes the following steps：
（1）According to mass ratio it is 1 by quick lime and 55 DEG C of hot water:4, which are added digestion reactor, carries out digestion reaction, cleans, stands
It is aged 40h, it is 1.065 to be diluted to proportion, obtains lime slurry；
（2）Lime slurry is delivered to carbonation reaction tower, carbon dioxide is passed through and carries out carburizing reagent, be added in carbonisation
Chemical additives and dispersant, carbonization to pH value are 7.5, and stopping is passed through carbon dioxide, and the specific surface area for controlling calcium carbonate is
38.9m2/ g obtains nano-calcium carbonate slurry；The chemical additives are 1 by mass ratio:2 phytic acid and tartaric acid composition, adds
Enter 1.2% that amount is calcium carbonate dry weight；The dispersant is 2 by mass ratio:1 polyoxyethylene glycerol ether monostearate
With the sulfonated rilanit special composition of succinate, addition is the 3% of calcium carbonate dry weight；
（3）Nano-calcium carbonate slurry is delivered to ultrasonic stirrer, and is heated to 80 DEG C, it is 2 to add by mass ratio:1 oil
The surface conditioning agent of sour diglycollic amide borate and octaphenyl cagelike silsesquioxane composition, the addition of surface conditioning agent are
The 1.5% of calcium carbonate dry weight is stirred by ultrasonic 45min, obtains modified nano calcium carbonate slurry；
（4）Modified nano calcium carbonate slurry dry, pulverize to get modified nano calcium carbonate again.
The coupling agent is 3 by mass ratio:1 aluminium methacrylate-zirconium coupling agent and rare-earth coupling agent composition.The friendship
It is 1 to join agent by mass ratio:1 starch sulfonic group succinate and polyacrylamide composition.The antiseptic is by chitosan and two
Cerium oxide forms.The processing aid is 1 by mass ratio:3 ricinoleic acid butyl ester sodium sulphate and poly- aminopropyltriethoxy sesquialter silicon
Oxygen alkane forms.
The preparation method of the modified calcium carbonate filled PVC tubing, includes the following steps：
S1:Each raw material is weighed according to aforementioned proportion, polyvinyl chloride resin, bismaleimide, acrylic acid-maleic anhydride copolymer are added
Enter blender, is heated to 60 DEG C and stirs evenly, obtain hybrid resin；
S2:It is heated to 90 DEG C in hybrid resin, poly- aminopropyltriethoxy silsesquioxane, maleic acid castor oil ester and asbestos are added
Fiber is uniformly mixed, adds coupling agent, crosslinking agent, antioxidant, stabilizer, antiseptic and processing aid, is sufficiently mixed
It is even, obtain tubing base-material；
S3:Aforementioned tubes base-material is delivered to double screw extruder, extrusion forming at being 180-200 DEG C in temperature, cooling and shaping,
Up to PVC pipe.
Embodiment 5
A kind of modified calcium carbonate filled PVC tubing, includes the raw material of following parts by weight：100 parts of polyvinyl chloride resin, bismaleimide
8 parts of amine, 1 part of poly- aminopropyltriethoxy silsesquioxane, 2 parts of maleic acid castor oil ester, changes 3 parts of acrylic acid-maleic anhydride copolymer
15 parts of nano-calcium carbonate of property, 5 parts of asbestos fibre, 2 parts of coupling agent, 0.5 part of crosslinking agent, 1 part of 1010 antioxidant, Organotin Stabilized
4.5 parts of 1.2 parts of agent, 1.8 parts of antiseptic and processing aid.
The preparation of the modified calcium carbonate includes the following steps：
（1）According to mass ratio it is 1 by quick lime and 60 DEG C of hot water:5, which are added digestion reactor, carries out digestion reaction, cleans, stands
It is aged 36h, it is 1.070 to be diluted to proportion, obtains lime slurry；
（2）Lime slurry is delivered to carbonation reaction tower, carbon dioxide is passed through and carries out carburizing reagent, be added in carbonisation
Chemical additives and dispersant, carbonization to pH value are 7, and stopping is passed through carbon dioxide, and the specific surface area for controlling calcium carbonate is
43.2m2/ g obtains nano-calcium carbonate slurry；The chemical additives are 1 by mass ratio:3 phytic acid and tartaric acid composition, adds
Enter 1.5% that amount is calcium carbonate dry weight；The dispersant is 2 by mass ratio:1 polyoxyethylene glycerol ether monostearate
With the sulfonated rilanit special composition of succinate, addition is the 1.5% of calcium carbonate dry weight；
（3）Nano-calcium carbonate slurry is delivered to ultrasonic stirrer, and is heated to 70 DEG C, it is 1 to add by mass ratio:1 oil
The surface conditioning agent of sour diglycollic amide borate and octaphenyl cagelike silsesquioxane composition, the addition of surface conditioning agent are
The 2% of calcium carbonate dry weight is stirred by ultrasonic 60min, obtains modified nano calcium carbonate slurry；
（4）Modified nano calcium carbonate slurry dry, pulverize to get modified nano calcium carbonate again.
The coupling agent is 1 by mass ratio:2 aluminium methacrylate-zirconium coupling agent and rare-earth coupling agent composition.The friendship
It is 1 to join agent by mass ratio:2 starch sulfonic group succinate and polyacrylamide composition.The antiseptic is by chitosan and two
Cerium oxide forms.The processing aid is 1 by mass ratio:1 ricinoleic acid butyl ester sodium sulphate and poly- aminopropyltriethoxy sesquialter silicon
Oxygen alkane forms.
The preparation method of the modified calcium carbonate filled PVC tubing, includes the following steps：
S1:Each raw material is weighed according to aforementioned proportion, polyvinyl chloride resin, bismaleimide, acrylic acid-maleic anhydride copolymer are added
Enter blender, is heated to 80 DEG C and stirs evenly, obtain hybrid resin；
S2:It is heated to 100 DEG C in hybrid resin, poly- aminopropyltriethoxy silsesquioxane, maleic acid castor oil ester and stone is added
Cotton fiber is uniformly mixed, adds coupling agent, crosslinking agent, antioxidant, stabilizer, antiseptic and processing aid, be sufficiently mixed
Uniformly, tubing base-material is obtained；
S3:Aforementioned tubes base-material is delivered to double screw extruder, extrusion forming at being 180-200 DEG C in temperature, cooling and shaping,
Up to PVC pipe.
PVC pipe prepared by embodiment the 1-5 conventionally tensile strength of determination sample, bending strength, freely-supported
Beam notch impact strength, elongation at break %, softening temperature and and Escherichia coli sterilizing rate, test result are as shown in table 1 for 24 hours.
Table 1：The performance test results of PVC pipe of the present invention
It is learnt from above-mentioned test result, PVC pipe prepared by the present invention has high intensity, high tenacity, shock resistance strong, resistance to
Heat, the advantages that antimicrobial form is strong, wide market.
Claims (10)
1. a kind of modified calcium carbonate filled PVC tubing, it is characterised in that：The PVC pipe includes the raw material of following parts by weight：
100 parts of polyvinyl chloride resin, 5-10 parts of bismaleimide, 3-5 parts of acrylic acid-maleic anhydride copolymer, poly- aminopropyltriethoxy sesquialter silicon
1-3 parts of oxygen alkane, 1-2 parts of maleic acid castor oil ester, 15-30 parts of modified nano calcium carbonate, 3-5 parts of asbestos fibre, coupling agent 1-3
Part, 0.5-2 parts of crosslinking agent, 0.5-1.5 parts of antioxidant, 0.5-1.5 parts of stabilizer, 1-2 parts of antiseptic and processing aid 3-5
Part.
2. modified calcium carbonate filled PVC tubing according to claim 1, it is characterised in that：The preparation of the modified calcium carbonate
Include the following steps：
Digestion reactor is added in quick lime and hot water and carries out digestion reaction, removal of impurities is still aging, and dilution obtains lime slurry；
Lime slurry is delivered to carbonation reaction tower, carbon dioxide is passed through and carries out carburizing reagent, is added in carbonisation brilliant
Type controlling agent and dispersant, carbonization to pH value are 6.5-7.5, and stopping is passed through carbon dioxide, and controls the specific surface area of calcium carbonate
For 30-50m2/ g obtains nano-calcium carbonate slurry；The chemical additives are made of phytic acid and tartaric acid, and addition is carbonic acid
The 0.5-1.5% of calcium dry weight；The dispersant is by polyoxyethylene glycerol ether monostearate and the sulfonated hydrogenation of succinate
Castor oil forms, and addition is the 1.5-3% of calcium carbonate dry weight；
Nano-calcium carbonate slurry is delivered to ultrasonic stirrer, and is heated to 60-80 DEG C, is added by oleic acid diethyl amide
The addition of the surface conditioning agent of borate and octaphenyl cagelike silsesquioxane composition, surface conditioning agent is calcium carbonate dry base weight
The 1.5-3% of amount is stirred by ultrasonic 30-60min, obtains modified nano calcium carbonate slurry；
Modified nano calcium carbonate slurry dry, pulverize to get modified nano calcium carbonate again.
3. modified calcium carbonate filled PVC tubing according to claim 2, it is characterised in that：It is planted in the chemical additives
The mass ratio of acid and tartaric acid is 1:1-3.
4. modified calcium carbonate filled PVC tubing according to claim 2, it is characterised in that：The dispersant is by mass ratio
For 1-2:The 1 sulfonated rilanit special composition of polyoxyethylene glycerol ether monostearate and succinate.
5. modified calcium carbonate filled PVC tubing according to claim 2, it is characterised in that：It is oily in the surface conditioning agent
The mass ratio of sour diglycollic amide borate and octaphenyl cagelike silsesquioxane is 1-2:1.
6. modified calcium carbonate filled PVC tubing according to claim 1, it is characterised in that：The coupling agent is by methyl-prop
Olefin(e) acid aluminum-zirconium coupling agent and rare-earth coupling agent composition.
7. modified calcium carbonate filled PVC tubing according to claim 1, it is characterised in that：The crosslinking agent is by starch sulphur
Acidic group succinate and polyacrylamide composition.
8. modified calcium carbonate filled PVC tubing according to claim 1, it is characterised in that：The antiseptic by chitosan and
Ceria forms.
9. modified calcium carbonate filled PVC tubing according to claim 1, it is characterised in that：The processing aid is by castor oil
Acid butyl ester sodium sulphate and poly- aminopropyltriethoxy silsesquioxane composition.
10. the preparation method of modified calcium carbonate filled PVC tubing as described in claim 1, it is characterised in that：Including walking as follows
Suddenly：
S1:Each raw material is weighed according to aforementioned proportion, polyvinyl chloride resin, bismaleimide, acrylic acid-maleic anhydride copolymer are added
Enter blender, is heated to 60-80 DEG C and stirs evenly, obtain hybrid resin；
S2:80-100 DEG C is heated in hybrid resin, be added poly- aminopropyltriethoxy silsesquioxane, maleic acid castor oil ester and
Asbestos fibre is uniformly mixed, adds coupling agent, crosslinking agent, antioxidant, stabilizer, antiseptic and processing aid, fully mixed
It closes uniformly, obtains tubing base-material；
S3:Aforementioned tubes base-material is delivered to double screw extruder, extrusion forming at being 180-200 DEG C in temperature, cooling and shaping,
Up to PVC pipe.
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|---|---|---|---|
| CN201810714664.2A CN108504001A (en) | 2018-06-29 | 2018-06-29 | A kind of modified calcium carbonate filled PVC tubing and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109135343A (en) * | 2018-09-28 | 2019-01-04 | 贺州钟山县双文碳酸钙新材料有限公司 | Calcium carbonate surface modifying once-combined modifying agent and its application method |
| CN109135341A (en) * | 2018-09-28 | 2019-01-04 | 贺州钟山县双文碳酸钙新材料有限公司 | Secondary composite modifier and its application handled in calcium carbonate surface |
| CN110016198A (en) * | 2019-02-12 | 2019-07-16 | 威海金泰新材料科技有限公司 | A kind of flame-proof antibiotic modified resin and preparation method thereof, application |
| CN110951116A (en) * | 2019-12-20 | 2020-04-03 | 贺州钟山县双文碳酸钙新材料有限公司 | Modified calcium carbonate and high-performance plastic prepared from same |
| CN111704809A (en) * | 2020-06-12 | 2020-09-25 | 广西夏阳环保科技有限公司 | Method for preparing barium sulfate for plastics and paint |
| CN111943246A (en) * | 2020-07-07 | 2020-11-17 | 广西夏阳环保科技有限公司 | Preparation method and application of calcium carbonate special for waterproof breathable film |
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| CN113716593A (en) * | 2021-07-06 | 2021-11-30 | 广西田东民泰实业有限责任公司 | Preparation technology of special nano calcium carbonate for degrading plastics |
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| CN116376113A (en) * | 2023-04-18 | 2023-07-04 | 广东永轩纳米塑胶材料有限公司 | Modified calcium carbonate for biodegradable plastic and preparation method thereof |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109135341A (en) * | 2018-09-28 | 2019-01-04 | 贺州钟山县双文碳酸钙新材料有限公司 | Secondary composite modifier and its application handled in calcium carbonate surface |
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| CN110016198A (en) * | 2019-02-12 | 2019-07-16 | 威海金泰新材料科技有限公司 | A kind of flame-proof antibiotic modified resin and preparation method thereof, application |
| CN110951116A (en) * | 2019-12-20 | 2020-04-03 | 贺州钟山县双文碳酸钙新材料有限公司 | Modified calcium carbonate and high-performance plastic prepared from same |
| CN111704809A (en) * | 2020-06-12 | 2020-09-25 | 广西夏阳环保科技有限公司 | Method for preparing barium sulfate for plastics and paint |
| CN111943246A (en) * | 2020-07-07 | 2020-11-17 | 广西夏阳环保科技有限公司 | Preparation method and application of calcium carbonate special for waterproof breathable film |
| CN113248844B (en) * | 2021-06-03 | 2022-07-05 | 浙江德首新型建材有限公司 | Environment-friendly PVC pipe and production process thereof |
| CN113248844A (en) * | 2021-06-03 | 2021-08-13 | 浙江德首新型建材有限公司 | Environment-friendly PVC pipe and production process thereof |
| CN113185791A (en) * | 2021-06-10 | 2021-07-30 | 阜阳市宝发塑胶有限公司 | Environment-friendly high-toughness PVC (polyvinyl chloride) pipe and preparation process thereof |
| CN113527806A (en) * | 2021-06-25 | 2021-10-22 | 杭州联通管业有限公司 | Super-strong power communication tube and preparation method thereof |
| CN113716593A (en) * | 2021-07-06 | 2021-11-30 | 广西田东民泰实业有限责任公司 | Preparation technology of special nano calcium carbonate for degrading plastics |
| CN114854241A (en) * | 2022-04-22 | 2022-08-05 | 西安德润九州新材料有限公司 | Super-waterproof putty powder for interior walls |
| CN114854241B (en) * | 2022-04-22 | 2023-08-08 | 西安德润九州新材料有限公司 | Super-waterproof putty powder for interior wall |
| CN116376113A (en) * | 2023-04-18 | 2023-07-04 | 广东永轩纳米塑胶材料有限公司 | Modified calcium carbonate for biodegradable plastic and preparation method thereof |
| CN118640347A (en) * | 2024-08-13 | 2024-09-13 | 福州市规划设计研究院集团有限公司 | Assembled thermosetting drainage pipeline and preparation method thereof |
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