CN109054220A - A kind of preparation method of environment-friendlyweather-proof weather-proof type high light transmission PVC pipeline - Google Patents
A kind of preparation method of environment-friendlyweather-proof weather-proof type high light transmission PVC pipeline Download PDFInfo
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- CN109054220A CN109054220A CN201810638432.3A CN201810638432A CN109054220A CN 109054220 A CN109054220 A CN 109054220A CN 201810638432 A CN201810638432 A CN 201810638432A CN 109054220 A CN109054220 A CN 109054220A
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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
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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Abstract
The invention discloses a kind of preparation methods of environment-friendlyweather-proof weather-proof type high light transmission PVC pipeline, it is first by weight, it weighs polyvinyl chloride resin, nanometer calcium carbonate powder, nano rare earth compound stabilizer, esters of acrylic acid lubricating type plasticized modifier, reactive siloxane, PE wax etc. and is stirred and evenly mixed by high-speed mixer completion, reactive siloxane hydrolysis, obtains PVC mixed raw material；PVC mixed raw material is put into double screw extruder, and the reactive siloxane after nanometer grade calcium carbonate powder and hydrolysis begins to warm up dehydration graft reaction, then squeezes out, and cutting obtains product and is packaged.One aspect of the present invention makes various auxiliary agents are more uniform to be dispersed in polyvinyl chloride resin, another aspect nanometer calcium carbonate powder with reactive siloxane is anti-biochemical reacts, it is evenly distributed in polyvinyl chloride resin in a manner of chemical bonding, so that the mixture of entire formula system can preferably eliminate stress when product is bent closer to homogeneous polymer, nanometer calcium carbonate powder and esters of acrylic acid lubricating type plasticized modifier.
Description
Technical field
The present invention relates to a kind of preparation method of PVC product, in particular to a kind of environment-friendlyweather-proof weather-proof type high light transmission PVC pipeline
Preparation method.
Background technique
Polyvinyl chloride (PVC) is that a kind of yield is big, purposes is wide, high comprehensive performance general-purpose plastics, hard PVC pipeline because
Its high performance-price ratio and be widely used in the fields such as draining, cable jacket.In building house, because waste blocking drainage pipeline is normal
There is generation, is easy access, needed for visualization drainage pipeline is public；During house decoration, how to ensure hidden in wall
Cable secure in interior and plate is reliably one of most important focus of owner, and concealed work visualizes trend of the times, transparent electricity
Therefore power protecting pipe comes into being.
Ordinary soft clear PVC material usually passes through plasticizer, such as: dioctyl phthalate (DOP) or phthalic acid
Processing aid based on dibutyl ester (DBP) etc. obtains polyvinyl chloride resin modification.But shock strength is low under PVC room temperature, easily
The disadvantages of embrittlement, product is poor, intensity is not high, cold resistance is bad there is also the transparency.Production hard transparent PVC pipeline is big absolutely at present
Majority uses organic tin stabilizer, but tin is applied as heavy metal by limitation in American-European some countries, and organic tin is stablized
Agent can also release pungent smell in hard transparent pvc pipe production process, and harmful to health, environmental-protecting performance is poor.Also there is use
Calcium zinc stabilizer is used for transparent PVC formula, such as: a kind of transparent flame-retarding PVC composition that Chinese patent CN101768313A is announced
And preparation method thereof, use is exactly calcium zinc stabilizer, but since the thermal stability of calcium zinc stabilizer is not as good as organotin and lead
Salt stabilizing agent needs more dosages, this will make the transparency of product reduce and there is a problem of that mist degree is high, in addition, calcium zinc is steady
Determine the problem of there is also precipitations in agent production process.
For PVC because of itself macromolecule material characteristic, brittleness is larger, and there are embrittlement, corrugation and stress when piping articles are bent
The problems such as whitening not only seriously affects beauty, but also significantly reduces transparent effect.
In terms of overcoming the shortcomings of normal transparent PVC toughness of material, usually it is changed using PVC impact modifier
Property, principal item has haloflex (CPE), nitrile rubber (NBR), esters of acrylic acid rubber etc..But CPE is modified
The PVC material transparency arrived is poor, tensile strength is low, should not be used in PVC transparent article；And common nitrile rubber and propylene
Esters of gallic acid rubber all can cause the gained transparent PVC product transparency to be affected because being easy photodegradation containing insatiable hunger key component,
102775693 A of Chinese patent CN discloses a kind of transparent polyvinyl chloride composition and preparation method thereof, has used a kind of partial size
Small fully vulcanized powder rubber, obtained transparent polyvinyl chloride can not only increase in terms of light transmission, and have simultaneously
Excellent physical mechanical property, but mist degree is higher, and vulcanized rubber can give out peculiar smell, inadequate ring health care in process
Health.
In existing technical products PVC product preparation, only with the mode of physical blending, exist inside material system more
Micropore or microdefect, micropore or microdefect are easy to induce the generation of crazing or crackle under external force, thus while bending is easy
There is the problems such as stress whitening, corrugation, embrittlement.
The PVC product of prior art preparation, mostly can be in the presence of the transparency is low, mist degree is high, easy embrittlement, environmental-protecting performance is poor and answers
The problems such as power is whitened.
Summary of the invention
In view of the above technical problems, the purpose of the present invention is to provide a kind of systems of environment-friendlyweather-proof weather-proof type high light transmission PVC pipeline
Preparation Method, overcome light transmittance existing for existing PVC transparent pipeline is low, mist degree is high, environmental-protecting performance is poor, bending when easy embrittlement, corrugation
The problems such as with stress whitening, and improve the processing performance of existing product.
A kind of preparation method of the environment-friendlyweather-proof weather-proof type high light transmission PVC pipeline, which comprises the following steps:
S1 ingredient: various raw material by weight, weigh 100 parts of polyvinyl chloride resin, nanometer calcium carbonate powder 5 ~ 15 part, nanometer
3 ~ 5 parts of rare earth composite stabilizer, 3 ~ 8 parts of esters of acrylic acid lubricating type plasticized modifier, 0.2 ~ 0.8 part of reactive siloxane, PE
0.2 ~ 0.6 part of wax, 0.3 ~ 1 part of in-lubricant, 0.4 ~ 0.8 part of pentaerythritol esters modifying agent, 0 ~ 1 part of pigment；
S2 mixing: the raw material that ingredient is completed are stirred and evenly mixed by high-speed mixer completion, and mixing time is not less than 5min,
PVC mixed raw material is obtained, reactive siloxane hydrolyzes during being stirred；
S3, material extrusion molding；
S3.1, preheating prepare: starting double screw extruder, complete corresponding parameter setting by working process parameter requirement, equipment is pre-
Heat is to 80 DEG C or more；
S3.2, dehydration graft reaction: PVC mixed raw material is put into double screw extruder, is heated to PVC mixed raw material temperature
At 80 DEG C or more, wherein the reactive siloxane and nanometer grade calcium carbonate powder after hydrolysis begin to warm up dehydration graft reaction；
S3.3, continuous heating material extrusion: heating material extrusion is persistently carried out to PVC mixed raw material by double screw extruder, wherein hydrolyzing
Reactive siloxane and nanometer grade calcium carbonate powder continuous heating afterwards is dehydrated graft reaction；
S3.4, cooling and shaping: it is exported in double screw extruder, obtains molding environment-friendlyweather-proof weather-proof type high light transmission PVC product, water flowing is cold
But, it is cut by setting length with cutting machine, the environment-friendlyweather-proof weather-proof type high light transmission PVC product being segmented；
S4, sampling Detection；
S4.1, light transmittance and mist degree performance detection: according to " measurement of the transparent plastic light transmittance and mist degree " standard of GB/T 2410 into
Row detection, environment-friendlyweather-proof weather-proof type high light transmission PVC product iuuminting rate are greater than 90%, and mist degree is lower than 3%；
S4.2, flame-resistant insulation detection: according to JG 3050 " insulating electrical casing pipe and accessory for building " standard detection, environmental protection is resistance to
The insulation of time type high light transmission PVC product, flame retardant property reach Eligibility requirements；
S4.3, weatherability detection: according to GB/T16422.2 " plastics laboratory light source exposure test method part 2 xenon arc
Lamp " A method tested, ageing time is not less than 6000h, environment-friendlyweather-proof weather-proof type high light transmission PVC product by simply supported beam notch shock,
Strength retention ratio is not less than 75%；Environment-friendlyweather-proof weather-proof type high light transmission PVC product color difference △ E < 3；
S4.4, feature of environmental protection detection: according to European Union's REACH standard detection, environment-friendlyweather-proof weather-proof type high light transmission PVC product is not detected 168 kinds
Height concern substance；
S4.5, bending property detection: environment-friendlyweather-proof weather-proof type high light transmission PVC product carries out bend pipe test under -15 DEG C and conditions above,
Embrittlement, corrugation, blushing do not occur；
S5, product are packaged；
Graft reaction equation is as follows:
。
A kind of preparation method of environment-friendlyweather-proof weather-proof type high light transmission PVC pipeline, which is characterized in that the S2 material extrusion molding
Specific steps are as follows:
(1) double screw extruder heats up, and control one area temperature is 130 DEG C~150 DEG C, two area's temperature are 135 DEG C~160
DEG C, three area's temperature be 145 DEG C~170 DEG C, four area's temperature are 150 DEG C~180 DEG C；
(2) it is resistance to get environmental protection to be added at one time extrusion molding in the double screw extruder after step (1) heating for PVC mixture
Time type high light transmission PVC product；Wherein, the screw speed of double screw extruder is 10~40 revs/min, and charging revolving speed is 10~30
Rev/min.
A kind of preparation method of the environment-friendlyweather-proof weather-proof type high light transmission PVC pipeline, which is characterized in that the polyvinyl chloride resin by
The polyvinyl chloride resin of SG-5 type and SG-8 type composition；Wherein in polyvinyl chloride resin, the mass fraction of SG-5 type polyvinyl chloride resin is 30 ~ 70%.
A kind of preparation method of environment-friendlyweather-proof weather-proof type high light transmission PVC pipeline, which is characterized in that the nanometer calcium carbonate
The partial size of powder is less than 100nm, preferably less than 60nm.
A kind of preparation method of environment-friendlyweather-proof weather-proof type high light transmission PVC pipeline, which is characterized in that the reactive silicon oxygen
The form of alkane be pale fat body, molecular structural formula such as following formula:
(CH3)3SiO-[(CH3)2SiO]a[(CH3)(R1)SiO]b[(CH3)(R2)SiO]c[(CH3)(R3)SiO]d-Si(CH3)3
In formula, the integer of a, b, c and d expression 1 ~ 20 independent；
R1For-CnH2n, the integer of n expression 10~30；
R2For-CH2-CH2-Si(OC2H5)3；
R3For-C3H6O-(C2H4O)m- H, m indicate 10 ~ 30 integer.
The preparation method of a kind of environment-friendlyweather-proof weather-proof type high light transmission PVC pipeline, which is characterized in that the in-lubricant is
The inclined fatty acid complex ester of glycerol.
A kind of preparation method of environment-friendlyweather-proof weather-proof type high light transmission PVC pipeline, which is characterized in that step S1 ingredient mixing
In, the operating condition of high-speed mixer being stirred are as follows: the whipping temp of high-speed mixer be lower than 80 DEG C, with 700 ~ 800 turns/
After the revolving speed of minute stirs 3 ~ 6 minutes, then with revolving speed stirring 5 ~ 8 minutes of 1300 ~ 1500 revs/min.
The preparation method of a kind of environment-friendlyweather-proof weather-proof type high light transmission PVC pipeline, which is characterized in that the pigment is pigment
Blue or paratonere.
A kind of preparation method of environment-friendlyweather-proof weather-proof type high light transmission PVC pipeline, which is characterized in that the reactive silicon oxygen
The mass ratio of alkane and nanometer calcium carbonate powder is 0.8 ~ 1.2:20, preferably 1:20.
A kind of preparation method of environment-friendlyweather-proof weather-proof type high light transmission PVC pipeline, which is characterized in that the S2 material extrusion molding
Specific steps are as follows:
(1) double screw extruder heats up, and control one area temperature is 130 DEG C~150 DEG C, two area's temperature are 135 DEG C~160
DEG C, three area's temperature be 145 DEG C~170 DEG C, four area's temperature are 150 DEG C~180 DEG C；
(2) it is resistance to get environmental protection to be added at one time extrusion molding in the double screw extruder after step (1) heating for PVC mixture
Time type high light transmission PVC product；Wherein, the screw speed of double screw extruder is 10~40 revs/min, and charging revolving speed is 10~30
Rev/min.
A kind of preparation method of the environment-friendlyweather-proof weather-proof type high light transmission PVC pipeline, which is characterized in that the polyvinyl chloride resin by
The polyvinyl chloride resin of SG-5 type and SG-8 type composition；Wherein in polyvinyl chloride resin, the mass fraction of SG-5 type polyvinyl chloride resin is 30 ~ 70%.
A kind of preparation method of environment-friendlyweather-proof weather-proof type high light transmission PVC pipeline, which is characterized in that the nanometer calcium carbonate
The partial size of powder is less than 100nm, preferably less than 60nm.
A kind of preparation method of environment-friendlyweather-proof weather-proof type high light transmission PVC pipeline, which is characterized in that the reactive silicon oxygen
The form of alkane be pale fat body, molecular structural formula such as following formula:
(CH3)3SiO-[(CH3)2SiO]a[(CH3)(R1)SiO]b[(CH3)(R2)SiO]c[(CH3)(R3)SiO]d-Si(CH3)3
In formula, the integer of a, b, c and d expression 1 ~ 20 independent；
R1For-CnH2n, the integer of n expression 10~30；
R2For-CH2-CH2-Si(OC2H5)3；
R3For-C3H6O-(C2H4O)m- H, m indicate 10 ~ 30 integer.
The preparation method of a kind of environment-friendlyweather-proof weather-proof type high light transmission PVC pipeline, which is characterized in that the in-lubricant is
The inclined fatty acid complex ester of glycerol.
A kind of preparation method of environment-friendlyweather-proof weather-proof type high light transmission PVC pipeline, which is characterized in that step S1 ingredient mixing
In, the operating condition of high-speed mixer being stirred are as follows: the whipping temp of high-speed mixer be lower than 80 DEG C, with 700 ~ 800 turns/
After the revolving speed of minute stirs 3 ~ 6 minutes, then with revolving speed stirring 5 ~ 8 minutes of 1300 ~ 1500 revs/min.
The preparation method of a kind of environment-friendlyweather-proof weather-proof type high light transmission PVC pipeline, which is characterized in that the pigment is pigment
Blue or paratonere.
A kind of preparation method of environment-friendlyweather-proof weather-proof type high light transmission PVC pipeline, which is characterized in that the reactive silicon oxygen
The mass ratio of alkane and nanometer calcium carbonate powder is 0.8 ~ 1.2:20, preferably 1:20.
A kind of preparation method of environment-friendlyweather-proof weather-proof type high light transmission PVC pipeline, which is characterized in that the pentaerythritol ester
Class modifying agent, nontoxic, environmentally friendly, biodegradable, contained humidity has excellent lubricity, good high-temperature stable less than 5%
Property, low volatility, excellent viscosity temperature characteristic, good low-temperature characteristics；The nano rare earth compound stabilizer partial size is less than
100nm has heat-proof aging and uvioresistant dual property, asepsis environment-protecting and keeps moulded products transparent, can enhance the weather-proof of product
Property.
It is different from existing physical blending extrusion technology, the present invention carries out reactivity using twin-screw extrusion equipment and squeezes
Shaping pipe (pipe fitting injection molding) out occurs that above-mentioned material between component in the plasticizing extrusion system that screw rod and barrel form
Chemical reaction；During tube extrusion forms (pipe fitting injection molding), mixture is conveyed under the action of screw rod, mixes, is cut
It cuts, react, extrusion molding of conducting heat, the mutual channelling of material, the mixing of highly uniform distribution.
The principle of the present invention is: the present invention is Reaction extrusion, it is made with the plasticizing extrusion system that screw rod and barrel form
For flow reactor, will be moved into extruder through too low, the high PVC mixture being uniformly mixed, mixture is in twin-screw
The lower conveying of effect, mixing, shearing, reaction, heat transfer extrusion molding, the mutual channelling of material, further equally distributed mixing, in spiral shell
During bar acts on, the moisture contained in reactive siloxane, pentaerythritol esters modifying agent and nanometer calcium carbonate powder
Under conditions of the moisture of adsorption, certain temperature (>=80 DEG C), certain pressure (>=20MPa), reactive siloxane and nanometer
Calcium carbonate powder fully chemically reacts, and final nanometer calcium carbonate powder is evenly distributed on PVC in a manner of being chemically bonded
Mix species；Specially raw material is after high-speed mixer mixes, and into double screw extruder, mixture is under the action of screw rod
Conveying, mixing, shearing, nanometer calcium carbonate powder is bonded with reactive siloxane reaction during this, this makes nanometer
Calcium carbonate powder is evenly distributed in the matrix resin of mixture in a manner of being chemically bonded, and entire mixture is close to homogeneous shape
State, which enhance the rheological characteristics of mixture, after extrusion in double screw extruder, mixture more easy mold release, and the PVC of preparation
Product has preferable mechanical performance and translucency；In addition, nanometer calcium carbonate powder can be eliminated to a certain extent when product is bent
Stress, but the mode being commonly added in polyvinyl chloride resin, material are not easy to be formed homogeneously, easy to be there are micropore or micro- scarce inside system
It falls into, mechanical performance and translucency are poor, and raw material of the present invention also adds the preparation method of reactive siloxane and use, mixing
Object conveys under the action of twin-screw, mixes, shearing, extrusion molding of conducting heat, the mutual channelling of material, further equally distributed mixed
It closes, and this process is also beneficial to well reacting for nanometer calcium carbonate powder and reactive siloxane due to material Combination, two
Aspect makes that the PVC product being evenly distributed finally is made, and translucency and mechanical performance are all preferable.
Compared with the existing technology, what the present invention obtained has the beneficial effect that
1) PVC product prepared by the present invention is examined according to GB/T 2410 " measurement of transparent plastic light transmittance and mist degree " standard
It surveys, light transmittance is greater than 90%, and mist degree is lower than 3%, and index is much better than prior art products；
2) PVC product prepared by the present invention, according to JG 3050 " insulating electrical casing pipe and accessory for building " standard detection, absolutely
Edge (electric property), flame retardant property reach Eligibility requirements；
3) PVC product prepared by the present invention, according to GB/T16422.2 " plastics laboratory light source exposure test method-part 2-
Xenon arc lamp " A method tested, and the aging of product time is 6000h；Product of the present invention simply supported beam notch impact strength retention rate is higher than
75%, existing product is generally lower than 60% in the market；Product of the present invention color change (color difference) △ E < 3, existing product is general in the market
All over higher than 4；
4) 168 kinds high concern substance (SVHC) is not detected according to European Union's REACH standard detection in PVC product prepared by the present invention,
Safety and environmental protection；
5) PVC product of the present invention carries out bend pipe test, not embrittlement, wrinkle resistant, non-whitening under -15 DEG C and conditions above；This hair
On the one hand the preparation method of bright PVC makes various auxiliary agents are more uniform to be dispersed in polyvinyl chloride resin, another aspect nanometer calcium carbonate
Powder with reactive siloxane is anti-biochemical reacts, be evenly distributed in polyvinyl chloride resin in a manner of chemical bonding, so that entirely
The mixture of formula system is closer to homogeneous polymer, nanometer calcium carbonate powder and esters of acrylic acid lubricating type plasticized modifier energy
Preferably eliminate stress when product bending；
6) in the present invention, acrylics plasticized modifier has excellent metal-stripping, and reactive siloxane can effectively drop
Low PVC mixture melt and metal surface of processing equipment viscous force, PE wax are also beneficial to PVC product forming process metal release,
The selection of these components is all conducive to the demoulding during PVC formed product；Secondly, nanometer calcium carbonate powder is to be chemically bonded
Mode is evenly distributed in the matrix resin of mixture, enhances the rheological characteristic of mixture, this is also conducive to PVC formed product mistake
Demoulding in journey avoids the migration and precipitation of PVC product small molecular component；
7) present invention is Reaction extrusion, and can reaction effectively be sufficiently carried out, and depends on PVC mixture melt temperature, pressure
And viscosity, wherein reactive siloxane can reduce the viscosity of PVC mixture melt, in favor of the abundant progress of reaction, this hair
The bright process parameters range defined: area's temperature is 130 DEG C~150 DEG C, two area's temperature are 135 DEG C~160 DEG C, three area's temperature
It is 150 DEG C~180 DEG C for 145 DEG C~170 DEG C, four area's temperature, host electric current 18~26 A, 20~30MPa of melt pressure.
Specific embodiment
The present invention is further explained in the light of specific embodiments, but the scope of protection of the present invention is not limited thereto.
In the present invention, nano rare earth compound stabilizer (being purchased from Baotou tombar thite institute), esters of acrylic acid lubricating type increase
Tough modifying agent (being purchased from Dow Dow company), reactive siloxane (being purchased from Danyang Jing Du optical material Co., Ltd), season penta
The agent of tetrol esters modification (is purchased from Hangzhou Jin Cheng auxiliary agent Co., Ltd).
Embodiment 1:
In the present invention, nano rare earth compound stabilizer (being purchased from Baotou tombar thite institute), esters of acrylic acid lubricating type toughening change
Property agent (be purchased from Dow Dow company), reactive siloxane (being purchased from Danyang Jing Du optical material Co., Ltd), pentaerythrite
Esters modification agent (is purchased from Hangzhou Jin Cheng auxiliary agent Co., Ltd).
Embodiment 1:
A kind of environment-friendlyweather-proof weather-proof type high light transmission PVC pipeline product is prepared, is grouped as by the group of following parts by weight:
50 parts of polyvinyl chloride resin (model SG-5)
50 parts of polyvinyl chloride resin (model SG-8)
8 parts of nanometer grade calcium carbonate powder (partial size is less than 100nm)
3.6 parts of nano rare earth compound stabilizer
6 parts of esters of acrylic acid lubricating type plasticized modifier
0.4 part of reactive siloxane
0.3 part of PE wax
0.5 part of the inclined fatty acid complex ester of glycerol
0.6 part of pentaerythritol esters modifying agent；
The form of the reactive siloxane is pale fat body, molecular structural formula are as follows:
(CH3)3SiO-[(CH3)2SiO]a[(CH3)(R1)SiO]b[(CH3)(R2)SiO]c[(CH3)(R3)SiO]d-Si(CH3)3
In formula, the integer of a, b, c and d expression 1 ~ 20 independent；R1For-CnH2n, the integer of n expression 10~30；R2
For-CH2-CH2-Si(OC2H5)3；R3For-C3H6O-(C2H4O)m- H, m indicate 10 ~ 30 integer, upper in the embodiment of the present invention
As long as stating parameter arbitrary value in the range of restriction to be ok, specific molecular formula is write out in order to prove it with corresponding official
It can roll into a ball, can be carried out chemical reaction, following embodiment is also identical, and the raw material that the present invention uses is commercial product, therefore, does not have to spy
Fixed limit determines the specific value of each parameter；
8) said components are mixed by weight, is put into high-speed mixer together and is stirred, the whipping temp of high-speed mixer
Lower than 80 DEG C, after being stirred 3 ~ 6 minutes with 700 ~ 800 revs/min of revolving speed, then with 1300 ~ 1500 revs/min of revolving speed stirring 5 ~
8 minutes, PVC mixture is obtained, property moves into double screw extruder again, and 135 DEG C of one area's temperature of control, two area's temperature are
145 DEG C, three area's temperature be 160 DEG C, four area's temperature are 170 DEG C, host electric current 18~26 A, 20~30MPa of melt pressure, with
Screw speed is 25 revs/min, charging revolving speed is extrusion molding under conditions of 20 revs/min, obtains environment-friendlyweather-proof weather-proof type high light transmission
PVC pipeline product.
Embodiment 2:
A kind of environment-friendlyweather-proof weather-proof type high light transmission PVC pipeline product is prepared, is grouped as by the group of following parts by weight:
40 parts of polyvinyl chloride resin (model SG-5)
60 parts of polyvinyl chloride resin (model SG-8)
10 parts of nanometer grade calcium carbonate powder (partial size is less than 100nm)
3.4 parts of nano rare earth compound stabilizer
7 parts of esters of acrylic acid lubricating type plasticized modifier
0.5 part of reactive siloxane
0.4 part of PE wax
0.6 part of the inclined fatty acid complex ester of glycerol
0.7 part of pentaerythritol esters modifying agent；
The form of the reactive siloxane is pale fat body, molecular structural formula are as follows:
(CH3)3SiO-[(CH3)2SiO]a[(CH3)(R1)SiO]b[(CH3)(R2)SiO]c[(CH3)(R3)SiO]d-Si(CH3)3；
Said components are mixed by weight, high-speed mixer is put into together and is stirred, are put into high-speed mixer stirring together
Mixing, 60 DEG C of the whipping temp of high-speed mixer, after being stirred 3 ~ 6 minutes with 700 ~ 800 revs/min of revolving speed, then with 1300 ~
1500 revs/min of revolving speed stirs 5 ~ 8 minutes, obtains PVC mixture, and property moves into double screw extruder again, control one
140 DEG C of area's temperature, two area's temperature are 150 DEG C, three area's temperature are 160 DEG C, four area's temperature are 175 DEG C, 18~26 A of host electric current,
20~30MPa of melt pressure is 28 revs/min in screw speed, and charging revolving speed is extrusion molding under conditions of 22 revs/min,
Obtain environment-friendlyweather-proof weather-proof type high light transmission PVC pipeline product.
Embodiment 3:
A kind of environment-friendlyweather-proof weather-proof type high light transmission PVC pipeline product is prepared, is grouped as by the group of following parts by weight:
60 parts of polyvinyl chloride resin (model SG-5)
40 parts of polyvinyl chloride resin (model SG-8)
6 parts of nanometer grade calcium carbonate powder (partial size is less than 100nm)
3 parts of nano rare earth compound stabilizer
8 parts of esters of acrylic acid lubricating type plasticized modifier
0.3 part of reactive siloxane
0.5 part of PE wax
0.4 part of the inclined fatty acid complex ester of glycerol
0.5 part of pentaerythritol esters modifying agent；
The form of the reactive siloxane is pale fat body, molecular structural formula are as follows:
(CH3)3SiO-[(CH3)2SiO]a[(CH3)(R1)SiO]b[(CH3)(R2)SiO]c[(CH3)(R3)SiO]d-Si(CH3)3；
Said components are mixed by weight, high-speed mixer is put into together and is stirred, are put into high-speed mixer stirring together
Mixing, 70 DEG C of the whipping temp of high-speed mixer, after being stirred 3 ~ 6 minutes with 700 ~ 800 revs/min of revolving speed, then with 1300 ~
1500 revs/min of revolving speed stirs 5 ~ 8 minutes, obtains PVC mixture, and property moves into double screw extruder again, control one
138 DEG C of area's temperature, two area's temperature are 145 DEG C, three area's temperature are 155 DEG C, four area's temperature are 170 DEG C, 18~26 A of host electric current,
20~30MPa of melt pressure, extrusion molding under conditions of screw speed is 23 revs/min, charging revolving speed is 20 revs/min,
Obtain environment-friendlyweather-proof weather-proof type high light transmission PVC pipeline product.
Comparative example 1:
Using the formula announced in the embodiment 1 of 101967251 A of Chinese patent CN as comparative example, the weight of various composition is matched
Than as follows:
100 parts of polyvinyl chloride
7.0 parts of novel transparent impact modifier
2 parts of organo-tin het stabilizer
1 part of OK-60
1 part of OK-74
0.15 part of polyethylene wax
High-speed mixer high speed is added by above-mentioned formula rate in various raw materials to mix, discharge cooling after reaching 120 DEG C,
Obtain poly (vinyl chloride) blend.The mixture is added at one time in double screw extruder again, controls 135 DEG C of area's temperature, two
Area's temperature is 145 DEG C, three area's temperature are 160 DEG C, four area's temperature are 170 DEG C, 18~26 A of host electric current, melt pressure 20~
30MPa, screw speed are 25 revs/min, and extrusion molding is under conditions of charging revolving speed is 20 revs/min to get PVC product.
Test example 1:
Embodiment 1 ~ 3, the PVC product of the preparation of comparative example 1 and commercially available PVC product (are originated from into wealth pipeline science and technology share in Zhejiang
Co., Ltd) it is tested for the property, test result is as shown in table 1；
Wherein, the detection of transparency, mist degree, according to GB/T 2410 " measurement of transparent plastic light transmittance and mist degree " standard；
The detection of flame retardant property, electric property, according to JG 3050 " insulating electrical casing pipe and accessory for building " standard；
The detection of weather resistance (impact strength retention rate and color difference), according to GB/T16422.2 " plastics laboratory light source exposure examination
Proved recipe method-part 2-xenon arc lamp " A method tested；
The detection of bending property, according to JG 3050 " insulating electrical casing pipe and accessory for building " standard；
The detection of environmental-protecting performance, according to European Union's REACH standard；
The performance test results of each PVC product of table 1
By 1 testing result of table it is found that PVC product prepared by the present invention, compared with prior art products, light transmittance, mist degree, ring
Guaranteed cost, bending property, weather resistance all have significant advantage.
To PVC product prepared by embodiment 1, according to GB/T16422.2 " plastics laboratory light source exposure test method-the 2
Partially-xenon arc lamp " A method tested, ageing time 6000h.
Content described in this specification is only to enumerate to inventive concept way of realization, and protection scope of the present invention is not answered
When the concrete form for being seen as limited by embodiment and being stated.
Claims (10)
1. a kind of preparation method of environment-friendlyweather-proof weather-proof type high light transmission PVC pipeline, which comprises the following steps:
S1 ingredient: various raw material by weight, weigh 100 parts of polyvinyl chloride resin, nanometer calcium carbonate powder 5 ~ 15 part, nanometer
3 ~ 5 parts of rare earth composite stabilizer, 3 ~ 8 parts of esters of acrylic acid lubricating type plasticized modifier, 0.2 ~ 0.8 part of reactive siloxane, PE
0.2 ~ 0.6 part of wax, 0.3 ~ 1 part of in-lubricant, 0.4 ~ 0.8 part of pentaerythritol esters modifying agent, 0 ~ 1 part of pigment；
S2 mixing: the raw material that ingredient is completed are stirred and evenly mixed by high-speed mixer completion, and mixing time is not less than 5min,
PVC mixed raw material is obtained, reactive siloxane hydrolyzes during being stirred；
S3, material extrusion molding；
S3.1, preheating prepare: starting double screw extruder, complete corresponding parameter setting by working process parameter requirement, equipment is pre-
Heat is to 80 DEG C or more；
S3.2, dehydration graft reaction: PVC mixed raw material is put into double screw extruder, is heated to PVC mixed raw material temperature
At 80 DEG C or more, wherein the reactive siloxane and nanometer grade calcium carbonate powder after hydrolysis begin to warm up dehydration graft reaction；
S3.3, continuous heating material extrusion: heating material extrusion is persistently carried out to PVC mixed raw material by double screw extruder, wherein hydrolyzing
Reactive siloxane and nanometer grade calcium carbonate powder continuous heating afterwards is dehydrated graft reaction；
S3.4, cooling and shaping: it is exported in double screw extruder, obtains molding environment-friendlyweather-proof weather-proof type high light transmission PVC product, water flowing is cold
But, it is cut by setting length with cutting machine, the environment-friendlyweather-proof weather-proof type high light transmission PVC product being segmented；
S4 product is packaged；
Graft reaction equation is as follows:
。
2. a kind of preparation method of environment-friendlyweather-proof weather-proof type high light transmission PVC pipeline according to claim 1, which is characterized in that institute
State the molding specific steps of S2 material extrusion are as follows:
(1) double screw extruder heats up, and control one area temperature is 130 DEG C~150 DEG C, two area's temperature are 135 DEG C~160
DEG C, three area's temperature be 145 DEG C~170 DEG C, four area's temperature are 150 DEG C~180 DEG C；
(2) it is resistance to get environmental protection to be added at one time extrusion molding in the double screw extruder after step (1) heating for PVC mixture
Time type high light transmission PVC product；Wherein, the screw speed of double screw extruder is 10~40 revs/min, and charging revolving speed is 10~30
Rev/min.
3. a kind of preparation method of environment-friendlyweather-proof weather-proof type high light transmission PVC pipeline according to claim 1, which is characterized in that institute
Polyvinyl chloride resin is stated to be made of the polyvinyl chloride resin of SG-5 type and SG-8 type；Wherein in polyvinyl chloride resin, the mass fraction of SG-5 type polyvinyl chloride resin
It is 30 ~ 70%.
4. a kind of preparation method of environment-friendlyweather-proof weather-proof type high light transmission PVC pipeline according to claim 1, which is characterized in that institute
The partial size for stating nanometer calcium carbonate powder is less than 100nm, preferably less than 60nm.
5. a kind of preparation method of environment-friendlyweather-proof weather-proof type high light transmission PVC pipeline according to claim 1, which is characterized in that institute
State reactive siloxane form be pale fat body, molecular structural formula such as following formula:
(CH3)3SiO-[(CH3)2SiO]a[(CH3)(R1)SiO]b[(CH3)(R2)SiO]c[(CH3)(R3)SiO]d-Si(CH3)3
In formula, the integer of a, b, c and d expression 1 ~ 20 independent；
R1For-CnH2n, the integer of n expression 10~30；
R2For-CH2-CH2-Si(OC2H5)3；
R3For-C3H6O-(C2H4O)m- H, m indicate 10 ~ 30 integer.
6. a kind of preparation method of environment-friendlyweather-proof weather-proof type high light transmission PVC pipeline according to claim 1, which is characterized in that institute
Stating in-lubricant is the inclined fatty acid complex ester of glycerol.
7. a kind of preparation method of environment-friendlyweather-proof weather-proof type high light transmission PVC pipeline according to claim 1, which is characterized in that step
In rapid S1 ingredient mixing, the operating condition of high-speed mixer being stirred are as follows: the whipping temp of high-speed mixer is lower than 80 DEG C,
After being stirred 3 ~ 6 minutes with 700 ~ 800 revs/min of revolving speed, then with revolving speed stirring 5 ~ 8 minutes of 1300 ~ 1500 revs/min.
8. a kind of preparation method of environment-friendlyweather-proof weather-proof type high light transmission PVC pipeline according to claim 1, which is characterized in that institute
Stating pigment is pigment blue or paratonere.
9. a kind of preparation method of environment-friendlyweather-proof weather-proof type high light transmission PVC pipeline according to claim 1, which is characterized in that institute
The mass ratio for stating reactive siloxane and nanometer calcium carbonate powder is 0.8 ~ 1.2:20, preferably 1:20.
10. a kind of preparation method of environment-friendlyweather-proof weather-proof type high light transmission PVC pipeline according to claim 1, which is characterized in that institute
Pentaerythritol esters modifying agent contained humidity is stated less than 5%；The nano rare earth compound stabilizer partial size is less than 100nm.
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| CN112140577A (en) * | 2020-09-18 | 2020-12-29 | 福建师范大学福清分校 | Manufacturing method for stable production of wallboard |
| CN114702727A (en) * | 2022-03-11 | 2022-07-05 | 湖南联塑科技实业有限公司 | Modified calcium carbonate, lead-free fast-flow PVC-U drain pipe and preparation method thereof |
| CN117106268A (en) * | 2023-09-07 | 2023-11-24 | 杭州管康塑业有限公司 | High-impact-resistance high-weather-resistance PVC reinforced pipe and preparation method thereof |
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| CN112140577A (en) * | 2020-09-18 | 2020-12-29 | 福建师范大学福清分校 | Manufacturing method for stable production of wallboard |
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| CN114702727B (en) * | 2022-03-11 | 2024-05-31 | 湖南联塑科技实业有限公司 | Modified calcium carbonate, lead-free rapid-flow PVC-U drain pipe and preparation method thereof |
| CN117106268A (en) * | 2023-09-07 | 2023-11-24 | 杭州管康塑业有限公司 | High-impact-resistance high-weather-resistance PVC reinforced pipe and preparation method thereof |
| CN117106268B (en) * | 2023-09-07 | 2024-04-16 | 杭州管康塑业有限公司 | High-impact-resistance high-weather-resistance PVC reinforced pipe and preparation method thereof |
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| CN109054220B (en) | 2020-12-29 |
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