CN109337242A - The preparation method and applications of PVC calcium-plastic board material modified calcium carbonate - Google Patents
The preparation method and applications of PVC calcium-plastic board material modified calcium carbonate Download PDFInfo
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- CN109337242A CN109337242A CN201811137310.2A CN201811137310A CN109337242A CN 109337242 A CN109337242 A CN 109337242A CN 201811137310 A CN201811137310 A CN 201811137310A CN 109337242 A CN109337242 A CN 109337242A
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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
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention discloses a kind of preparation method and applications of PVC calcium-plastic board material modified calcium carbonate, belong to calcium carbonate modified and applied technical field, the modified calcium carbonate is by twice-modified preparation, the PVC calcium-plastic board material, as unit of parts by weight, including following raw material: 22-30 parts of polyvinyl chloride resin, 65-82 parts of modified calcium carbonate, 18-25 parts of wood powder, 2-4 parts of heat stabilizer, 3-5 parts of processing aid, 0.4-2.3 parts of stearic acid, 0.5-1.6 parts of polyethylene wax, 0.8-5 parts of semi-refined paraffin wax, toughener 4-7 parts, 2-3 parts of lubricant of plasticising.Using PVC calcium-plastic board material made of modified calcium carbonate, the tensile strength, bending strength, impact strength, oxygen index (OI), coarse whiting loading of plate can be improved, reduce production cost.
Description
[technical field]
The invention belongs to calcium carbonate modified and applied technical fields, and in particular to a kind of modified carbonic acid of PVC calcium-plastic board material
The preparation method and applications of calcium.
[background technique]
Calcic-plastic composite material is to be equipped with one kind composite material made of polyvinyl chloride resin is kneaded using inorganic calcium salt as primary raw material.Have
Chemical stability, high-low temperature resistant have good thermal insulation, water resistance, there is good anti-flammability, and burning velocity is slow, and smoke is few,
It is not easy to cause fire, public hazards.It is widely used as construction material, fitment material for family, furniture and consumer goods materials etc..
Calcium carbonate is a kind of common inorganic filler, because source is wide, cheap etc., be widely used in plastics, rubber, coating,
The fields such as plate.But calcium carbonate surface is hydrophilic and oleophobic, easily reunite between large specific surface area, surface energy height, particle, when direct or big
When in amount filling organic basis material, not only it is difficult to be uniformly dispersed, and very weak with the binding force of matrix, two-phase interface is caused to lack
It falls into, the decline of certain performances of composite material.Therefore, in order to widen its application field, it is necessary to be modified, make to calcium carbonate surface
Its surface oleophilic drainage, the compatibility of enhancing and plate improve the dispersibility in organic basis material, improve compound
The performances such as tensile strength, bending strength, the impact strength of material reduce production cost.
[summary of the invention]
The technical problem to be solved in the present invention is to provide a kind of preparation method of PVC calcium-plastic board material modified calcium carbonate and its
Using to solve the problems, such as that calcium carbonate surface modifying, PVC calcium-plastic board material be fire-retardant, cost.
In order to solve the above technical problems, the invention adopts the following technical scheme:
A kind of preparation method of PVC calcium-plastic board material modified calcium carbonate, comprising the following steps:
S1: removing impurity thing after choosing the lime stone cleaning shipped from yard of material, and building stones are carried out to dry removing surface water
Point, then building stones are crushed with crusher, calcium carbonate fragment is made；
S2: calcium carbonate fragment made from step S1 is delivered into the synchronous addition sodium lignin sulfonate of vertical mill, polymerization
The grinding aid and grinding, the additional amount of the grinding aid of hydramine composition are the 2.3-3.5% of calcium carbonate breaking weight, and carbonic acid is made
Calcium microlith powder；
S3: calcium carbonate microlith powder made from step S2 is classified with grader, and the Paris white of 100-200 mesh is made
Body；
S4: once-combined modifying agent is added to calcium carbonate powder made from step S3, the once-combined modifying agent is by two
Glycollic amide glycerol stearate monoesters, dodecyl polyoxyethylene ether, two (2- ethylhexyl) hydroxysuccinic acid ester sodium sulfonate groups
At the additional amount of the once-combined modifying agent is the 1.2-1.8% of Paris white body weight, and grinding, it is 200- that partial size, which is made,
The mixture a of 400 mesh；
S5: mixture a made from step S4 and secondary composite modifier are added in blender, described secondary composite modified
Agent is made of siloxanes triol alginate esters, sodium glycocholate, chlordene tripolyphosphazene, methylene-bisacrylamide, described secondary compound
The additional amount of modifying agent is the 0.8-1.4% of Paris white body weight, stirs 30-40min with the speed of 2000-3000r/min,
Mixture b is made；
S6: it dries at being 42-53 DEG C in temperature by mixture b made from step S5 to water content≤0.4%, is ground to
PVC calcium-plastic board material modified calcium carbonate is made in 600-1000 mesh, sieving.
Preferably, the weight ratio of sodium lignin sulfonate described in step S2 and polyalcohol amine is 1:2.3-6.4.
Preferably, diglycollic amide glycerol stearate monoesters described in step S4, dodecyl polyoxyethylene ether and two (2-
Ethylhexyl) hydroxysuccinic acid ester sodium sulfonate weight ratio be 3.2-4:1:1.6-2.5.
Preferably, siloxanes triol alginate esters described in step S5, sodium glycocholate, chlordene tripolyphosphazene and di-2-ethylhexylphosphine oxide third
The weight ratio of acrylamide is 1.8-3:2.4-4.5:1:2-3.5.
The present invention also provides a kind of application of modified calcium carbonate in PVC calcium-plastic board material, the PVC calcium-plastic board material, with
Parts by weight are unit, including following raw material: 22-30 parts of polyvinyl chloride resin, 65-82 parts of modified calcium carbonate, 18-25 parts of wood powder, thermostabilization
2-4 parts of agent, 0.4-2.3 parts of stearic acid, 0.5-1.6 parts of polyethylene wax, 0.8-5 parts of semi-refined paraffin wax, increases 3-5 parts of processing aid
Toughener 4-7 parts, 2-3 parts of lubricant of modeling.
Preferably, the heat stabilizer is KSR organic RE compound stabilizer.
Preferably, the processing aid is processing aid ACR.
Preferably, the plasticising toughener is methyl methacrylate.
Preferably, the lubricant is pentaerythrite palmitate.
The present invention also provides a kind of preparation methods of PVC calcium-plastic board material, comprising the following steps:
S1: weighing above-mentioned each raw material according to above-mentioned formula, and high-speed mixer is added in each raw material, is warming up to 110-125 DEG C,
It is stirred evenly with the speed of 2000-3000r/min, obtains mixed material；
S2: being delivered to conical double screw extruder for mixed material made from step S1, squeezes at being 156-172 DEG C in temperature
It forms out, cooling and shaping, PVC calcium-plastic board material is made.
The invention has the following advantages:
(1) the data of embodiment 1-3 and comparative example 10 as it can be seen that utilizing PVC calcium-plastic board made of modified calcium carbonate
Material, tensile strength, bending strength, impact strength, oxygen index (OI), coarse whiting loading are significantly increased；By embodiment 1-3 and comparison
The data of example 11 are as it can be seen that the tensile strength, bending strength of PVC calcium-plastic board material made of the present invention, impact strength, oxygen index (OI), again
Calcium loading is superior to comparative example 11 (prior art), illustrates compared with prior art, the present invention having significant progress；By reality
The data of a 1-3 are applied as it can be seen that embodiment 2 is optimum embodiment.
(2) by embodiment 2 and the data of comparative example 1-5 as it can be seen that siloxanes triol alginate esters, sodium glycocholate, chlordene trimerization
Phosphonitrile, methylene-bisacrylamide play synergistic effect in calcium carbonate modified, and collaboration improves the stretching of PVC calcium-plastic board material
Intensity, bending strength, impact strength, oxygen index (OI)；This is: since siloxanes triol alginate esters are inorganic-organic hybridization structure, containing
There are silicon oxygen bond, hydroxyl, carboxyl, carbonyl, silicon oxygen bond, hydroxyl, carboxyl, carbonyl can be introduced on calcium carbonate particle surface when modified,
When PVC calcium-plastic board material is ignited, it is oxygen barrier, heat-insulated that siloxanes moves to rapidly PVC calcium-plastic board material surface property protective layer, prevents
The burning of plate；In addition, chlordene tripolyphosphazene makes it have P-N synergistic effect, siloxanes triol alginate esters cooperate chlordene trimerization
The use of phosphonitrile keeps the flame retardant effect of PVC calcium-plastic board material more significant, to improve the oxygen index (OI) of PVC calcium-plastic board material.Siloxanes
Triol alginate esters can form chemical bond with the hydroxyl on modified calcium carbonate powder surface for the first time, can further improve calcium carbonate
The tensile strength, bending strength, impact that PVC calcium-plastic board material can be improved is added in dispersibility and compatibility in polyvinyl chloride resin
Intensity.In addition calcium carbonate is modified by sodium glycocholate, methylene-bisacrylamide progress surface, sodium glycocholate, di-2-ethylhexylphosphine oxide third
Acrylamide contains carboxyl, sulfonic group, amino groups, can introduce the bases such as carboxyl, sulfonic group, amino on calcium carbonate particle surface
The compatibility, dispersibility and processing fluidity of calcium carbonate, each group and PVC calcium-plastic board material System forming not only can be improved in group
Network structure improves reaction system interfacial adhesion so that calcium carbonate and polyvinyl chloride resin have good compatibility, improves plate
Tensile strength, bending strength, impact strength.
(3) by embodiment 2 and the data of comparative example 6-9 as it can be seen that diglycollic amide glycerol stearate monoesters, dodecyl gather
Ethylene oxide ether, two (2- ethylhexyl) hydroxysuccinic acid ester sodium sulfonates play synergistic effect in calcium carbonate modified, and collaboration mentions
High tensile strength, bending strength, the impact strength of PVC calcium-plastic board material；This is: calcium carbonate first uses diglycollic amide stearic acid sweet
Oily monoesters, dodecyl polyoxyethylene ether, two (2- ethylhexyl) hydroxysuccinic acid ester sodium sulfonates carry out surface and are modified, due to two
Glycollic amide glycerol stearate monoesters, dodecyl polyoxyethylene ether, in two (2- ethylhexyl) hydroxysuccinic acid ester sodium sulfonates
Containing groups such as Long carbon chain fatty acid, hydroxyl, carboxyl, carbonyl, sulfonic groups, can when first time is modified calcium carbonate particle surface
Carboxyl, sulfonic group, amino groups are introduced, the compatibility, dispersibility and processing fluidity with calcium carbonate not only can be improved, respectively
Group and PVC calcium-plastic board material System forming network structure, so that calcium carbonate and polyvinyl chloride resin and wood powder have good compatibility,
PVC calcium-plastic board material reaction system interfacial adhesion is improved, and then improves tensile strength, bending strength, the impact strength of plate.
(4) data comparison of embodiment 1-3 and comparative example 1-11 utilizes PVC calcium-plastic board made of modified calcium carbonate
Material, not only tensile strength, bending strength, impact strength, oxygen index (OI) increase, but also coarse whiting loading also increases；This
The coarse whiting loading > 50wt% of PVC calcium-plastic board material made of inventive embodiments 1-3, be much better than the prior art (comparative example 11
Coarse whiting loading < 35wt%), it is seen that it is greatly increased using the usage amount of calcium carbonate in technique of the invention, it in this way can be very big
Production cost is reduced, is increased economic efficiency.
[specific embodiment]
To facilitate a better understanding of the present invention, it is illustrated by the following examples, these examples belong to protection of the invention
Range, but do not limit the scope of the invention.
In embodiment, the preparation method of the PVC calcium-plastic board material modified calcium carbonate, comprising the following steps:
S1: removing impurity thing after choosing the lime stone cleaning shipped from yard of material, and building stones are carried out to dry removing surface water
Point, then building stones are crushed with crusher, calcium carbonate fragment is made；
S2: calcium carbonate fragment made from step S1 is delivered into the synchronous addition sodium lignin sulfonate of vertical mill, polymerization
The grinding aid of hydramine composition and grinding, the additional amount of the grinding aid is the 2.3-3.5% of calcium carbonate breaking weight, described wooden
The weight ratio of plain sodium sulfonate and polyalcohol amine is 1:2.3-6.4, and calcium carbonate microlith powder is made；
S3: calcium carbonate microlith powder made from step S2 is classified with grader, and the Paris white of 100-200 mesh is made
Body；
S4: once-combined modifying agent is added to calcium carbonate powder made from step S3, the once-combined modifying agent is by two
Glycollic amide glycerol stearate monoesters, dodecyl polyoxyethylene ether, two (2- ethylhexyl) hydroxysuccinic acid ester sodium sulfonate groups
At the additional amount of the once-combined modifying agent is the 1.2-1.8% of Paris white body weight, the diglycollic amide stearic acid
The weight ratio of monoglyceride, dodecyl polyoxyethylene ether and two (2- ethylhexyl) hydroxysuccinic acid ester sodium sulfonates is 3.2-4:
The mixture a that partial size is 200-400 mesh is made in 1:1.6-2.5, grinding；
S5: mixture a made from step S4 and secondary composite modifier are added in blender, described secondary composite modified
Agent is made of siloxanes triol alginate esters, sodium glycocholate, chlordene tripolyphosphazene, methylene-bisacrylamide, described secondary compound
The additional amount of modifying agent is the 0.8-1.4% of Paris white body weight, the siloxanes triol alginate esters, sodium glycocholate, chlordene
The weight ratio of tripolyphosphazene and methylene-bisacrylamide is 1.8-3:2.4-4.5:1:2-3.5, with 2000-3000r/min's
Speed stirs 30-40min, and mixture b is made；
S6: it dries at being 42-53 DEG C in temperature by mixture b made from step S5 to water content≤0.4%, is ground to
PVC calcium-plastic board material modified calcium carbonate is made in 600-1000 mesh, sieving.
Application of the modified calcium carbonate in PVC calcium-plastic board material, the PVC calcium-plastic board material, as unit of parts by weight, including
Following raw material: 22-30 parts of polyvinyl chloride resin, 65-82 parts of modified calcium carbonate, 18-25 parts of wood powder, 2-4 parts of heat stabilizer, processing aid
3-5 parts, 0.4-2.3 parts of stearic acid, 0.5-1.6 parts of polyethylene wax, 0.8-5 parts of semi-refined paraffin wax, toughener 4-7 parts of plasticising, profit
2-3 parts of lubrication prescription.
The heat stabilizer is KSR organic RE compound stabilizer.
The processing aid is processing aid ACR.
The plasticising toughener is methyl methacrylate.
The lubricant is pentaerythrite palmitate.
The preparation method of PVC calcium-plastic board material, comprising the following steps:
S1: weighing above-mentioned each raw material according to above-mentioned formula, and high-speed mixer is added in each raw material, is warming up to 110-125 DEG C,
It is stirred evenly with the speed of 2000-3000r/min, obtains mixed material；
S2: being delivered to conical double screw extruder for mixed material made from step S1, squeezes at being 156-172 DEG C in temperature
It forms out, cooling and shaping, PVC calcium-plastic board material is made.
Below by more specifically examples illustrate the present invention.
Embodiment 1
A kind of preparation method of PVC calcium-plastic board material modified calcium carbonate, comprising the following steps:
S1: removing impurity thing after choosing the lime stone cleaning shipped from yard of material, and building stones are carried out to dry removing surface water
Point, then building stones are crushed with crusher, calcium carbonate fragment is made；
S2: calcium carbonate fragment made from step S1 is delivered into the synchronous addition sodium lignin sulfonate of vertical mill, polymerization
The grinding aid and grinding, the additional amount of the grinding aid of hydramine composition are the 2.5% of calcium carbonate breaking weight, the sulfomethylated lignin
The weight ratio of sour sodium and polyalcohol amine is 1:2.8, and calcium carbonate microlith powder is made；
S3: calcium carbonate microlith powder made from step S2 is classified with grader, and the calcium carbonate powder of 100 mesh is made；
S4: once-combined modifying agent is added to calcium carbonate powder made from step S3, the once-combined modifying agent is by two
Glycollic amide glycerol stearate monoesters, dodecyl polyoxyethylene ether, two (2- ethylhexyl) hydroxysuccinic acid ester sodium sulfonate groups
At the additional amount of the once-combined modifying agent is the 1.3% of Paris white body weight, the diglycollic amide glycerol stearate
The weight ratio of monoesters, dodecyl polyoxyethylene ether and two (2- ethylhexyl) hydroxysuccinic acid ester sodium sulfonates is 3.2:1:1.8,
The mixture a that partial size is 200 mesh is made in grinding；
S5: mixture a made from step S4 and secondary composite modifier are added in blender, described secondary composite modified
Agent is made of siloxanes triol alginate esters, sodium glycocholate, chlordene tripolyphosphazene, methylene-bisacrylamide, described secondary compound
The additional amount of modifying agent is the 1% of Paris white body weight, the siloxanes triol alginate esters, sodium glycocholate, chlordene trimerization phosphorus
The weight ratio of nitrile and methylene-bisacrylamide is 1.8:2.4:1:2, stirs 40min with the speed of 2000r/min, mixing is made
Object b；
S6: drying at being 42 DEG C in temperature by mixture b made from step S5 to water content is 0.4%, is ground to 600
PVC calcium-plastic board material modified calcium carbonate is made in mesh, sieving.
Application of the modified calcium carbonate in PVC calcium-plastic board material, the PVC calcium-plastic board material, as unit of parts by weight, including
Following raw material: 30 parts of polyvinyl chloride resin, 65 parts of modified calcium carbonate, 18 parts of wood powder, 2 parts of heat stabilizer, 3 parts of processing aid, stearic acid
0.4 part, 0.6 part of polyethylene wax, 1 part of semi-refined paraffin wax, plasticising 4 parts of toughener, 2 parts of lubricant.
The heat stabilizer is KSR organic RE compound stabilizer.
The processing aid is processing aid ACR.
The plasticising toughener is methyl methacrylate.
The lubricant is pentaerythrite palmitate.
The preparation method of PVC calcium-plastic board material, comprising the following steps:
S1: weighing above-mentioned each raw material according to above-mentioned formula, and high-speed mixer is added in each raw material, is warming up to 110 DEG C, with
The speed of 2000r/min stirs evenly, and obtains mixed material；
S2: being delivered to conical double screw extruder for mixed material made from step S1, is extruded at being 158 DEG C in temperature
PVC calcium-plastic board material is made in type, cooling and shaping.
Embodiment 2
A kind of preparation method of PVC calcium-plastic board material modified calcium carbonate, comprising the following steps:
S1: removing impurity thing after choosing the lime stone cleaning shipped from yard of material, and building stones are carried out to dry removing surface water
Point, then building stones are crushed with crusher, calcium carbonate fragment is made；
S2: calcium carbonate fragment made from step S1 is delivered into the synchronous addition sodium lignin sulfonate of vertical mill, polymerization
The grinding aid and grinding, the additional amount of the grinding aid of hydramine composition are the 3.2% of calcium carbonate breaking weight, the sulfomethylated lignin
The weight ratio of sour sodium and polyalcohol amine is 1:4.6, and calcium carbonate microlith powder is made；
S3: calcium carbonate microlith powder made from step S2 is classified with grader, and the calcium carbonate powder of 200 mesh is made；
S4: once-combined modifying agent is added to calcium carbonate powder made from step S3, the once-combined modifying agent is by two
Glycollic amide glycerol stearate monoesters, dodecyl polyoxyethylene ether, two (2- ethylhexyl) hydroxysuccinic acid ester sodium sulfonate groups
At the additional amount of the once-combined modifying agent is the 1.5% of Paris white body weight, the diglycollic amide glycerol stearate
The weight ratio of monoesters, dodecyl polyoxyethylene ether and two (2- ethylhexyl) hydroxysuccinic acid ester sodium sulfonates is 3.5:1:2.3,
The mixture a that partial size is 300 mesh is made in grinding；
S5: mixture a made from step S4 and secondary composite modifier are added in blender, described secondary composite modified
Agent is made of siloxanes triol alginate esters, sodium glycocholate, chlordene tripolyphosphazene, methylene-bisacrylamide, described secondary compound
The additional amount of modifying agent is the 1.2% of Paris white body weight, the siloxanes triol alginate esters, sodium glycocholate, chlordene trimerization
The weight ratio of phosphonitrile and methylene-bisacrylamide is 2.6:3.7:1:3.2, stirs 30min with the speed of 3000r/min, is made
Mixture b；
S6: drying at being 50 DEG C in temperature by mixture b made from step S5 to water content is 0.3%, is ground to 800
PVC calcium-plastic board material modified calcium carbonate is made in mesh, sieving.
Application of the modified calcium carbonate in PVC calcium-plastic board material, the PVC calcium-plastic board material, as unit of parts by weight, including
Following raw material: 25 parts of polyvinyl chloride resin, 80 parts of modified calcium carbonate, 20 parts of wood powder, 3 parts of heat stabilizer, 4 parts of processing aid, stearic acid
1.6 parts, 1.2 parts of polyethylene wax, 4 parts of semi-refined paraffin wax, plasticising 6 parts of toughener, 2.5 parts of lubricant.
The heat stabilizer is KSR organic RE compound stabilizer.
The processing aid is processing aid ACR.
The plasticising toughener is methyl methacrylate.
The lubricant is pentaerythrite palmitate.
The preparation method of PVC calcium-plastic board material, comprising the following steps:
S1: weighing above-mentioned each raw material according to above-mentioned formula, and high-speed mixer is added in each raw material, is warming up to 120 DEG C, with
The speed of 3000r/min stirs evenly, and obtains mixed material；
S2: being delivered to conical double screw extruder for mixed material made from step S1, is extruded at being 170 DEG C in temperature
PVC calcium-plastic board material is made in type, cooling and shaping.
Embodiment 3
A kind of preparation method of PVC calcium-plastic board material modified calcium carbonate, comprising the following steps:
S1: removing impurity thing after choosing the lime stone cleaning shipped from yard of material, and building stones are carried out to dry removing surface water
Point, then building stones are crushed with crusher, calcium carbonate fragment is made；
S2: calcium carbonate fragment made from step S1 is delivered into the synchronous addition sodium lignin sulfonate of vertical mill, polymerization
The grinding aid and grinding, the additional amount of the grinding aid of hydramine composition are the 3.2% of calcium carbonate breaking weight, the sulfomethylated lignin
The weight ratio of sour sodium and polyalcohol amine is 1:4.8, and calcium carbonate microlith powder is made；
S3: calcium carbonate microlith powder made from step S2 is classified with grader, and the calcium carbonate powder of 100 mesh is made；
S4: once-combined modifying agent is added to calcium carbonate powder made from step S3, the once-combined modifying agent is by two
Glycollic amide glycerol stearate monoesters, dodecyl polyoxyethylene ether, two (2- ethylhexyl) hydroxysuccinic acid ester sodium sulfonate groups
At the additional amount of the once-combined modifying agent is the 1.8% of Paris white body weight, the diglycollic amide glycerol stearate
The weight ratio of monoesters, dodecyl polyoxyethylene ether and two (2- ethylhexyl) hydroxysuccinic acid ester sodium sulfonates is 4:1:2.5, is ground
The mixture a that partial size is 400 mesh is made in mill；
S5: mixture a made from step S4 and secondary composite modifier are added in blender, described secondary composite modified
Agent is made of siloxanes triol alginate esters, sodium glycocholate, chlordene tripolyphosphazene, methylene-bisacrylamide, described secondary compound
The additional amount of modifying agent is the 1.4% of Paris white body weight, the siloxanes triol alginate esters, sodium glycocholate, chlordene trimerization
The weight ratio of phosphonitrile and methylene-bisacrylamide is 3:4.5:1:3.5, stirs 30min with the speed of 3000r/min, is made mixed
Close object b；
S6: drying at being 53 DEG C in temperature by mixture b made from step S5 to water content is 0.4%, is ground to 1000
PVC calcium-plastic board material modified calcium carbonate is made in mesh, sieving.
Application of the modified calcium carbonate in PVC calcium-plastic board material, the PVC calcium-plastic board material, as unit of parts by weight, including
Following raw material: 28 parts of polyvinyl chloride resin, 75 parts of modified calcium carbonate, 18 parts of wood powder, 4 parts of heat stabilizer, 4 parts of processing aid, stearic acid 2
Part, 1.5 parts of polyethylene wax, 4.5 parts of semi-refined paraffin wax, plasticising 7 parts of toughener, 3 parts of lubricant.
The heat stabilizer is KSR organic RE compound stabilizer.
The processing aid is processing aid ACR.
The plasticising toughener is methyl methacrylate.
The lubricant is pentaerythrite palmitate.
The preparation method of PVC calcium-plastic board material, comprising the following steps:
S1: weighing above-mentioned each raw material according to above-mentioned formula, and high-speed mixer is added in each raw material, is warming up to 125 DEG C, with
The speed of 2000r/min stirs evenly, and obtains mixed material；
S2: being delivered to conical double screw extruder for mixed material made from step S1, is extruded at being 172 DEG C in temperature
PVC calcium-plastic board material is made in type, cooling and shaping.
Comparative example 1
Modified calcium carbonate preparation process and the preparation process of embodiment 2 are essentially identical, have only the difference is that only carrying out step
The modification of S4, and the modification without step S5.
Comparative example 2
Modified calcium carbonate preparation process and the preparation process of embodiment 2 are essentially identical, have only unlike secondary compound change
Lack siloxanes triol alginate esters in property agent.
Comparative example 3
Modified calcium carbonate preparation process and the preparation process of embodiment 2 are essentially identical, have only unlike secondary compound change
Lack sodium glycocholate in property agent.
Comparative example 4
Modified calcium carbonate preparation process and the preparation process of embodiment 2 are essentially identical, have only unlike secondary compound change
Lack chlordene tripolyphosphazene in property agent.
Comparative example 5
Modified calcium carbonate preparation process and the preparation process of embodiment 2 are essentially identical, have only unlike secondary compound change
Lack methylene-bisacrylamide in property agent.
Comparative example 6
Modified calcium carbonate preparation process and the preparation process of embodiment 2 are essentially identical, have only the difference is that without step
The modification of S4, but it is directly entered the modification of step S5.
Comparative example 7
Modified calcium carbonate preparation process and the preparation process of embodiment 2 are essentially identical, have only the difference is that once-combined change
Lack diglycollic amide glycerol stearate monoesters in property agent.
Comparative example 8
Modified calcium carbonate preparation process and the preparation process of embodiment 2 are essentially identical, have only the difference is that once-combined change
Lack dodecyl polyoxyethylene ether in property agent.
Comparative example 9
Modified calcium carbonate preparation process and the preparation process of embodiment 2 are essentially identical, have only the difference is that once-combined change
Lack two (2- ethylhexyl) hydroxysuccinic acid ester sodium sulfonates in property agent.
Comparative example 10
This comparative example example and embodiment 2 the difference is that: without the modification of step S4 and step S5.
Comparative example 11
Using patent document " a kind of diatomite calcium plastic panel and its production method (Authorization Notice No.:
CN104072908B) " method of embodiment 1-5 prepares PVC calcium-plastic board material.
By embodiment 1-3 and comparative example 1-11 prepare PVC calcium-plastic board material conventionally measure batten tensile strength,
Bending strength, impact strength, oxygen index (OI), coarse whiting loading, test result is as follows shown in table.
As seen from the above table: (1) by the data of embodiment 1-3 and comparative example 10 as it can be seen that being made using modified calcium carbonate
PVC calcium-plastic board material, tensile strength, bending strength, impact strength, oxygen index (OI), coarse whiting loading are significantly increased；By implementing
The data of example 1-3 and comparative example 11 are as it can be seen that the tensile strength, bending strength of PVC calcium-plastic board material made of the present invention, impact are strong
Degree, oxygen index (OI), coarse whiting loading are superior to comparative example 11 (prior art), illustrate compared with prior art, the present invention having aobvious
The progress of work；By the data of embodiment 1-3 as it can be seen that embodiment 2 is optimum embodiment.
(2) by embodiment 2 and the data of comparative example 1-5 as it can be seen that siloxanes triol alginate esters, sodium glycocholate, chlordene trimerization
Phosphonitrile, methylene-bisacrylamide play synergistic effect in calcium carbonate modified, and collaboration improves the stretching of PVC calcium-plastic board material
Intensity, bending strength, impact strength, oxygen index (OI)；This is: since siloxanes triol alginate esters are inorganic-organic hybridization structure, containing
There are silicon oxygen bond, hydroxyl, carboxyl, carbonyl, silicon oxygen bond, hydroxyl, carboxyl, carbonyl can be introduced on calcium carbonate particle surface when modified,
When PVC calcium-plastic board material is ignited, it is oxygen barrier, heat-insulated that siloxanes moves to rapidly PVC calcium-plastic board material surface property protective layer, prevents
The burning of plate；In addition, chlordene tripolyphosphazene makes it have P-N synergistic effect, siloxanes triol alginate esters cooperate chlordene trimerization
The use of phosphonitrile keeps the flame retardant effect of PVC calcium-plastic board material more significant, to improve the oxygen index (OI) of PVC calcium-plastic board material.Siloxanes
Triol alginate esters can form chemical bond with the hydroxyl on modified calcium carbonate powder surface for the first time, can further improve calcium carbonate
The tensile strength, bending strength, impact that PVC calcium-plastic board material can be improved is added in dispersibility and compatibility in polyvinyl chloride resin
Intensity.In addition calcium carbonate is modified by sodium glycocholate, methylene-bisacrylamide progress surface, sodium glycocholate, di-2-ethylhexylphosphine oxide third
Acrylamide contains carboxyl, sulfonic group, amino groups, can introduce the bases such as carboxyl, sulfonic group, amino on calcium carbonate particle surface
The compatibility, dispersibility and processing fluidity of calcium carbonate, each group and PVC calcium-plastic board material System forming not only can be improved in group
Network structure improves reaction system interfacial adhesion so that calcium carbonate and polyvinyl chloride resin have good compatibility, improves plate
Tensile strength, bending strength, impact strength.
(3) by embodiment 2 and the data of comparative example 6-9 as it can be seen that diglycollic amide glycerol stearate monoesters, dodecyl gather
Ethylene oxide ether, two (2- ethylhexyl) hydroxysuccinic acid ester sodium sulfonates play synergistic effect in calcium carbonate modified, and collaboration mentions
High tensile strength, bending strength, the impact strength of PVC calcium-plastic board material；This is: calcium carbonate first uses diglycollic amide stearic acid sweet
Oily monoesters, dodecyl polyoxyethylene ether, two (2- ethylhexyl) hydroxysuccinic acid ester sodium sulfonates carry out surface and are modified, due to two
Glycollic amide glycerol stearate monoesters, dodecyl polyoxyethylene ether, in two (2- ethylhexyl) hydroxysuccinic acid ester sodium sulfonates
Containing groups such as Long carbon chain fatty acid, hydroxyl, carboxyl, carbonyl, sulfonic groups, can when first time is modified calcium carbonate particle surface
Carboxyl, sulfonic group, amino groups are introduced, the compatibility, dispersibility and processing fluidity with calcium carbonate not only can be improved, respectively
Group and PVC calcium-plastic board material System forming network structure, so that calcium carbonate and polyvinyl chloride resin and wood powder have good compatibility,
PVC calcium-plastic board material reaction system interfacial adhesion is improved, and then improves tensile strength, bending strength, the impact strength of plate.
(4) data comparison of embodiment 1-3 and comparative example 1-11 utilizes PVC calcium-plastic board made of modified calcium carbonate
Material, not only tensile strength, bending strength, impact strength, oxygen index (OI) increase, but also coarse whiting loading also increases；This
The coarse whiting loading > 50wt% of PVC calcium-plastic board material made of inventive embodiments 1-3, be much better than the prior art (comparative example 11
Coarse whiting loading < 35wt%), it is seen that it is greatly increased using the usage amount of calcium carbonate in technique of the invention, it in this way can be very big
Production cost is reduced, is increased economic efficiency.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of PVC calcium-plastic board material modified calcium carbonate, which comprises the following steps:
S1: impurity thing is removed after choosing the lime stone cleaning shipped from yard of material, building stones are carried out to dry removing surface moisture, so
Building stones are crushed with crusher afterwards, calcium carbonate fragment is made；
S2: calcium carbonate fragment made from step S1 is delivered into the synchronous addition sodium lignin sulfonate, polyalcohol amine of vertical mill
The grinding aid and grinding, the additional amount of the grinding aid of composition are the 2.3-3.5% of calcium carbonate breaking weight, and it is thin that calcium carbonate is made
Mountain flour；
S3: calcium carbonate microlith powder made from step S2 is classified with grader, and the calcium carbonate powder of 100-200 mesh is made；
S4: once-combined modifying agent is added to calcium carbonate powder made from step S3, the once-combined modifying agent is by diethanol
Amide glycerol stearate monoesters, dodecyl polyoxyethylene ether, two (2- ethylhexyl) hydroxysuccinic acid ester sodium sulfonates composition, institute
The additional amount for stating once-combined modifying agent is the 1.2-1.8% of Paris white body weight, and grinding, it is 200-400 mesh that partial size, which is made,
Mixture a；
S5: mixture a made from step S4 and secondary composite modifier are added in blender, the secondary composite modifier by
Siloxanes triol alginate esters, sodium glycocholate, chlordene tripolyphosphazene, methylene-bisacrylamide composition, it is described secondary composite modified
The additional amount of agent is the 0.8-1.4% of Paris white body weight, stirs 30-40min with the speed of 2000-3000r/min, is made
Mixture b；
S6: it dries at being 42-53 DEG C in temperature by mixture b made from step S5 to water content≤0.4%, is ground to 600-
PVC calcium-plastic board material modified calcium carbonate is made in 1000 mesh, sieving.
2. according to the preparation method of PVC calcium-plastic board material modified calcium carbonate described in right 1, it is characterised in that: described in step S2
The weight ratio of sodium lignin sulfonate and polyalcohol amine is 1:2.3-6.4.
3. according to the preparation method of PVC calcium-plastic board material modified calcium carbonate described in right 1, it is characterised in that: described in step S4
Diglycollic amide glycerol stearate monoesters, dodecyl polyoxyethylene ether and two (2- ethylhexyl) hydroxysuccinic acid ester sodium sulfonates
Weight ratio be 3.2-4:1:1.6-2.5.
4. according to the preparation method of PVC calcium-plastic board material modified calcium carbonate described in right 1, it is characterised in that: described in step S5
Siloxanes triol alginate esters, sodium glycocholate, chlordene tripolyphosphazene and methylene-bisacrylamide weight ratio be 1.8-3:2.4-
4.5:1:2-3.5。
5. a kind of application of modified calcium carbonate according to claim 1 in PVC calcium-plastic board material, which is characterized in that described
PVC calcium-plastic board material, as unit of parts by weight, including following raw material: 22-30 parts of polyvinyl chloride resin, 65-82 parts of modified calcium carbonate, wood
18-25 parts of powder, 2-4 parts of heat stabilizer, 3-5 parts of processing aid, 0.4-2.3 parts of stearic acid, 0.5-1.6 parts of polyethylene wax, half essence
Paraffin 0.8-5 parts of refining, toughener 4-7 parts, 2-3 parts of lubricant of plasticising.
6. according to application of the modified calcium carbonate described in right 5 in PVC calcium-plastic board material, it is characterised in that: the heat stabilizer
For KSR organic RE compound stabilizer.
7. according to application of the modified calcium carbonate described in right 5 in PVC calcium-plastic board material, it is characterised in that: the processing aid
For processing aid ACR.
8. according to application of the modified calcium carbonate described in right 5 in PVC calcium-plastic board material, it is characterised in that: the plasticising toughening
Agent is methyl methacrylate.
9. according to application of the modified calcium carbonate described in right 5 in PVC calcium-plastic board material, it is characterised in that: the lubricant is
Pentaerythrite palmitate.
10. a kind of preparation method of PVC calcium-plastic board material as claimed in claim 5, it is characterised in that: the following steps are included:
S1: weighing above-mentioned each raw material according to above-mentioned formula, and high-speed mixer is added in each raw material, is warming up to 110-125 DEG C, with
The speed of 2000-3000r/min stirs evenly, and obtains mixed material；
S2: being delivered to conical double screw extruder for mixed material made from step S1, is extruded at being 156-172 DEG C in temperature
PVC calcium-plastic board material is made in type, cooling and shaping.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110773301A (en) * | 2019-11-13 | 2020-02-11 | 山西宇皓环保纸业有限公司 | Special ground calcium carbonate powder for stone paper, preparation method and stone paper |
| CN115109452A (en) * | 2022-07-22 | 2022-09-27 | 广西福宝信科技有限公司 | Modified calcium carbonate, preparation method and application thereof in production of antibacterial powder coating |
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| CN105038028A (en) * | 2015-08-06 | 2015-11-11 | 什邡市格瑞装饰材料科技有限公司 | Ecological wood marble-imitated plate and manufacturing method thereof |
| CN107501891A (en) * | 2017-09-08 | 2017-12-22 | 贺州钟山县双文碳酸钙新材料有限公司 | A kind of application of modified calcium carbonate in the plastic |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105038028A (en) * | 2015-08-06 | 2015-11-11 | 什邡市格瑞装饰材料科技有限公司 | Ecological wood marble-imitated plate and manufacturing method thereof |
| CN107501891A (en) * | 2017-09-08 | 2017-12-22 | 贺州钟山县双文碳酸钙新材料有限公司 | A kind of application of modified calcium carbonate in the plastic |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110773301A (en) * | 2019-11-13 | 2020-02-11 | 山西宇皓环保纸业有限公司 | Special ground calcium carbonate powder for stone paper, preparation method and stone paper |
| CN115109452A (en) * | 2022-07-22 | 2022-09-27 | 广西福宝信科技有限公司 | Modified calcium carbonate, preparation method and application thereof in production of antibacterial powder coating |
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Application publication date: 20190215 |