CN116023748B - High-strength plastic sound tube and its production process - Google Patents

High-strength plastic sound tube and its production process Download PDF

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CN116023748B
CN116023748B CN202310101516.4A CN202310101516A CN116023748B CN 116023748 B CN116023748 B CN 116023748B CN 202310101516 A CN202310101516 A CN 202310101516A CN 116023748 B CN116023748 B CN 116023748B
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acr
modifier
pvc resin
mbs
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CN116023748A (en
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孙丽华
孙丽娟
殷震宇
李勤
陆晓燕
吴江东
殷铄涵
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Jiangsu Nobel Plastics Co ltd
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Jiangsu Nobel Plastics Co ltd
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Abstract

The application relates to the technical field of plastics, and particularly discloses a high-strength plastic acoustic tube and a production process thereof, wherein the plastic acoustic tube comprises the following raw materials in parts by weight: 100 parts of PVC resin, 2-4 parts of ACR impact modifier, 0.6-1.4 parts of organotin stabilizer, 5-8 parts of MBS modifier, 0.1-0.3 part of oxidized polyethylene wax, 0.2-0.5 part of calcium stearate, 0.3-0.7 part of polyethylene wax, 3-8 parts of nano calcium carbonate and 0.2-0.5 part of processing modifier; the plastic acoustic tube has the advantages of simple formula and strict proportion, and has remarkable tensile property and shock resistance. The production process of the plastic acoustic tube comprises the following steps: firstly, uniformly mixing the raw materials according to a formula, plasticizing and extruding, then carrying out two-way stretching for two times, and finally carrying out surface treatment and cutting; the prepared plastic acoustic pipe has excellent comprehensive performance and can be better applied to pile foundation detection.

Description

High-strength plastic sound tube and its production process
Technical Field
The application relates to the technical field of plastics, in particular to a high-strength plastic sound tube and a production process thereof.
Background
The sound tube is also called sound wave detecting tube, the quality of a pile can be detected by utilizing the sound tube, and the sound tube is a channel for a probe to enter the pile body when the filling pile is subjected to ultrasonic detection, so that the sound tube is an important component of an ultrasonic detection system of the filling pile, and the pre-burying mode of the sound tube in the pile, the arrangement mode of the sound tube on the cross section of the pile and the selection of the sound tube material can directly influence the detection result.
The acoustic tube is made of steel and plastic, and the steel tube has the defects of high density and high construction difficulty, is easy to corrode and can cause water leakage and tube blockage; the acoustic tube made of plastic materials has the advantages of low density, corrosion resistance and the like, the PVC tube is a tube made of thermoplastic high polymer formed by polymerizing vinyl chloride monomers at present, but in the production of the PVC tube, the radial performance of the PVC tube can be enhanced through the self-reinforcing effect of a biaxial stretching process while the axial performance of the tube is maintained, but the ductility of the PVC tube is generally insufficient and the brittleness is larger, the PVC tube is difficult to adapt to the processing of the biaxial stretching self-reinforcing PVC tube, the impact resistance of the PVC tube is reduced, and the PVC tube is seriously restricted to be widely applied to the acoustic tube. Therefore, it is needed to provide a high-strength plastic sound tube and a production process thereof, so as to solve the problem of lower impact resistance of the PVC tube, make the performance of the plastic sound tube more excellent, and be better applied to pile foundation detection.
Disclosure of Invention
In order to solve the problem of lower impact resistance of the existing PVC pipe, the application provides a high-strength plastic sound tube and a production process thereof.
In a first aspect, the present application provides a high-strength plastic acoustic tube, which adopts the following technical scheme:
The high-strength plastic sound tube comprises the following raw materials in parts by weight: 100 parts of PVC resin, 2-4 parts of ACR impact modifier, 0.6-1.4 parts of organic tin stabilizer, 5-8 parts of MBS modifier, 0.1-0.3 part of oxidized polyethylene wax, 0.2-0.5 part of calcium stearate, 0.3-0.7 part of polyethylene wax, 3-8 parts of nano calcium carbonate and 0.2-0.5 part of processing modifier.
According to the technical scheme, the PVC resin, the ACR impact modifier, the organotin stabilizer, the MBS modifier, the oxidized polyethylene wax, the calcium stearate, the polyethylene wax, the nano calcium carbonate and the processing modifier are used as main raw materials to prepare the high-strength plastic sound measuring tube, and the components interact with each other, so that the plastic sound measuring tube has remarkable impact resistance, has higher tensile strength and can be better applied to pile foundation detection.
Preferably, the ACR impact modifier comprises the following raw materials in parts by weight: 10-20 parts of ACR seed emulsion, 20-30 parts of ethyl acrylate, 0.6-1 part of allyl methacrylate, 1-2 parts of diallyl phthalate, 0.5-0.9 part of sophorolipid, 0.05-0.1 part of cumene hydroperoxide, 5-7 parts of nano silicon dioxide, 1-3 parts of organic bentonite, 0.01-0.05 part of demulsifier and 40-60 parts of water.
Preferably, the ACR-based impact modifier is prepared by the following process:
S11, adding ACR seed emulsion, ethyl acrylate, diallyl phthalate, sophorolipid and cumene hydroperoxide into water, performing ultrasonic dispersion for 40-60min, heating to 50-70 ℃ under the protection of nitrogen, and performing heat preservation reaction for 1-3h to obtain ACR emulsion;
S12, adding allyl methacrylate, nano silicon dioxide and organic bentonite into the ACR emulsion obtained in the step S11, fully reacting for 1-2 hours at 75-85 ℃, adding a demulsifier, washing with water and drying to obtain the ACR impact modifier.
According to the technical scheme, under the action of the ACR seed emulsion, cumene hydroperoxide is used as an initiator, ethyl acrylate and diallyl phthalate are polymerized to obtain the ACR emulsion with a core-shell structure, then allyl methacrylate is added into the ACR emulsion to further polymerize, so that a shell layer forms a compact network structure, and meanwhile, nano silicon dioxide and organic bentonite are also added, so that the strength of the shell layer can be improved, and various process parameters are controlled, so that the shock resistance of the ACR impact modifier is more excellent, and the impact toughness of a plastic sound tube is remarkably improved.
Preferably, the ACR seed emulsion comprises the following raw materials in parts by weight: 30-40 parts of butyl acrylate, 6-10 parts of neopentyl glycol diacrylate, 0.5-0.9 part of sodium polystyrene sulfonate, 0.02-0.08 part of sodium persulfate and 30-40 parts of water.
Preferably, the ACR seed emulsion is prepared by the following method:
Adding butyl acrylate, neopentyl glycol diacrylate, sodium persulfate and sodium polystyrene sulfonate into water, uniformly mixing for 30-60min at the rotating speed of 2000-3000r/min, heating to 40-70 ℃ under the protection of nitrogen, reacting for 2-4h, and cooling to 20-30 ℃ to obtain the ACR seed emulsion.
By adopting the technical scheme, the application takes butyl acrylate and neopentyl glycol diacrylate as main raw materials, and under the action of an initiator sodium persulfate and an emulsifier sodium polystyrene sulfonate, the butyl acrylate and the neopentyl glycol diacrylate can be polymerized to form a nuclear monomer, and simultaneously, the process parameters are controlled, so that the solid content of emulsion particles in the emulsion is improved, the size of the emulsion particles is moderate, and the ACR seed emulsion with more stable performance is obtained.
Preferably, the PVC resin is further pretreated:
Firstly, treating PVC resin by using plasma at 50-70 ℃, uniformly mixing the PVC resin and a solvent according to the mass ratio of 1:4-6, standing and swelling for 1-2h, evaporating the solvent at 110-120 ℃, and then, keeping warm, standing and aging for 3-4h to obtain an aged material; and drying and crushing the aged material to obtain the pretreated PVC resin.
By adopting the technical scheme, the PVC resin is firstly treated by adopting the plasma, so that a large number of active groups appear on the surface of the PVC resin, and the binding force with other components can be enhanced; swelling by using a solvent, wherein solvent molecules can permeate between PVC resin crystallization network chain segments, and after the solvent volatilizes, a plurality of tiny gaps are formed inside the PVC resin; in the blending system, the components with smaller volume can enter the PVC resin for filling, so that the mechanical property of the plastic sound tube is enhanced.
Preferably, the solvent is obtained by mixing diethyl ether and tetrahydrofuran in a mass ratio of 3-7:5.
By adopting the technical scheme, the PVC resin swelling agent takes the mixture of diethyl ether and tetrahydrofuran as the solvent, and the polarity of the diethyl ether and the polarity of the tetrahydrofuran are different, and the polarity of the diethyl ether and the polarity of the tetrahydrofuran are synergistic, so that the PVC resin can be swelled, and the swelling effect of the PVC is good.
Preferably, the organotin stabilizer is methyl tin mercaptide and/or dibutyl tin maleate.
By adopting the technical scheme, the organotin stabilizer is methyl tin mercaptide and/or dibutyl tin maleate, and the organotin stabilizer and the dibutyl tin maleate have chelation, so that the components are mixed more uniformly and plasticized more fully; therefore, the addition of the organotin stabilizer can lead the plastic acoustic tube to have excellent mechanical properties, and particularly the impact strength is obviously improved.
Preferably, the MBS modifier is prepared by mixing MBS M-41 and MBS B-521 in a mass ratio of 5:4-9.
By adopting the technical scheme, the MBS modifier is prepared by mixing MBS M-41 and MBS B-521 in a certain mass ratio, and the MBS M-41 and the MBS B-521 are mutually assisted, have good compatibility when being blended with PVC, promote a blending system to be more stable, further improve the impact resistance of the PVC, and simultaneously promote the disintegration and further gelation of the PVC resin through the excellent friction performance of the MBS modifier, and improve the processability of the PVC resin.
Preferably, the processing modifier is at least one of P-551J, JL-M01 and JL-G01 FX.
By adopting the technical scheme, the processing modifier is at least one of P-551J, JL-M01 and JL-G01FX, has good compatibility with a blending system, can increase the melt strength, reduce the melt viscosity, and improve the processing performance, thereby effectively improving the mechanical property of the plastic acoustic tube.
In a second aspect, the application provides a production process of a high-strength plastic acoustic tube, which adopts the following technical scheme:
The production process of the high-strength plastic sound tube comprises the following steps:
S1, uniformly mixing PVC resin, an organotin stabilizer, an ACR impact modifier, an MBS modifier, oxidized polyethylene wax, calcium stearate, polyethylene wax, nano calcium carbonate and a processing modifier according to a formula to obtain a mixed material; plasticizing and extruding the mixture to obtain a tube blank;
s2, performing two-way stretching on the tube blank to obtain a crude product; and (3) carrying out surface treatment and cutting on the crude product to obtain the high-strength plastic sound tube.
Preferably, in the step S1, the stirring is carried out for 10-30min at the rotating speed of 600-1000 r/min.
Preferably, the extrusion temperature in the step S1 is 170-200 ℃, and the extrusion screw speed is 8-10r/min.
Preferably, the specific operation of two biaxial stretching in step S2 is as follows: performing first biaxial stretching at 100-140deg.C with radial stretching ratio of 1.5-3, vacuum shaping, and cooling to 50-70deg.C; and heating to 90-100 ℃ for the second time, carrying out two-way stretching for the second time according to the circumferential stretching ratio of 1-2, carrying out vacuum shaping, and cooling to 20-30 ℃.
By adopting the technical scheme, the production process of the high-strength plastic acoustic tube comprises the steps of blending raw materials, plasticizing and extruding to obtain a tube blank, stretching the tube blank radially and circularly twice, and then carrying out surface treatment and cutting to obtain the high-strength plastic acoustic tube; according to the application, through two-time biaxial stretching, network-shaped molecular orientation is formed in the material, so that the internal stress is eliminated, and the impact strength of the plastic acoustic tube is improved; the method has simple production process steps and low cost, is suitable for industrial production, and the obtained high-strength plastic acoustic tube has more excellent comprehensive performance and wide market prospect.
In summary, the application has the following beneficial effects:
1. The plastic sound tube of the application takes PVC resin, an organotin stabilizer, an ACR impact modifier, an MBS modifier, oxidized polyethylene wax, calcium stearate, polyethylene wax, nano calcium carbonate and a processing modifier as raw materials, so that the plastic sound tube has excellent impact resistance and remarkable tensile property.
2. The ACR type impact modifier takes ACR seed emulsion, ethyl acrylate, allyl methacrylate, diallyl phthalate, cumene hydroperoxide, nano silicon dioxide and organic bentonite as main raw materials to prepare the ACR type impact modifier with a core-shell structure, and can obviously improve the impact resistance of a plastic sound measuring tube.
3. The MBS modifier is prepared by mixing MBS M-41 and MBS B-521 with certain mass, and the two are synergistic, so that the impact resistance of the plastic sound tube is greatly improved.
4. According to the production process of the plastic acoustic tube, after the raw materials are blended, plasticizing and extruding are carried out, so that a tube blank is obtained, the tube blank is stretched radially and circularly for two times, and vacuum setting is carried out, and the obtained plastic acoustic tube belongs to a PVC-0 tube and has more excellent comprehensive performance; the production process of the plastic acoustic tube has simple steps and low cost, is suitable for industrial production, and has wide market prospect.
Detailed Description
The present application will be described in further detail with reference to examples.
Preparation examples 1-5 provide ACR seed emulsions and methods of making the same.
Preparation example 1
The ACR seed emulsion comprises the following raw materials: 30g of butyl acrylate, 6g of neopentyl glycol diacrylate, 0.5g of sodium polystyrene sulfonate, 0.02g of sodium persulfate and 30g of water;
An ACR seed emulsion prepared by the method of:
Adding butyl acrylate, neopentyl glycol diacrylate, sodium persulfate and sodium polystyrene sulfonate into water, uniformly mixing for 60min at a rotating speed of 3000r/min, heating to 40 ℃ under the protection of nitrogen, reacting for 4h, and cooling to 20 ℃ to obtain the ACR seed emulsion.
Preparation example 2
The ACR seed emulsion comprises the following raw materials: 32g of butyl acrylate, 7g of neopentyl glycol diacrylate, 0.6g of sodium polystyrene sulfonate, 0.04g of sodium persulfate and 32g of water;
An ACR seed emulsion prepared by the method of:
adding butyl acrylate, neopentyl glycol diacrylate, sodium persulfate and sodium polystyrene sulfonate into water, uniformly mixing for 40min at the rotation speed of 2800r/min, heating to 45 ℃ under the protection of nitrogen, reacting for 3.5h, and cooling to 22 ℃ to obtain the ACR seed emulsion.
Preparation example 3
The ACR seed emulsion comprises the following raw materials: 35g of butyl acrylate, 8g of neopentyl glycol diacrylate, 0.7g of sodium polystyrene sulfonate, 0.05g of sodium persulfate and 35g of water;
An ACR seed emulsion prepared by the method of:
Adding butyl acrylate, neopentyl glycol diacrylate, sodium persulfate and sodium polystyrene sulfonate into water, uniformly mixing for 45min at the rotating speed of 2500r/min, heating to 50 ℃ under the protection of nitrogen, reacting for 3h, and cooling to 25 ℃ to obtain the ACR seed emulsion.
Preparation example 4
The ACR seed emulsion comprises the following raw materials: 38g of butyl acrylate, 9g of neopentyl glycol diacrylate, 0.8g of sodium polystyrene sulfonate, 0.06g of sodium persulfate and 38g of water;
An ACR seed emulsion prepared by the method of:
Adding butyl acrylate, neopentyl glycol diacrylate, sodium persulfate and sodium polystyrene sulfonate into water, uniformly mixing for 50min at the rotating speed of 2200r/min, heating to 60 ℃ under the protection of nitrogen, reacting for 2.5h, and cooling to 28 ℃ to obtain the ACR seed emulsion.
Preparation example 5
The ACR seed emulsion comprises the following raw materials: 40g of butyl acrylate, 10g of neopentyl glycol diacrylate, 0.9g of sodium polystyrene sulfonate, 0.08g of sodium persulfate and 40g of water;
An ACR seed emulsion prepared by the method of:
adding butyl acrylate, neopentyl glycol diacrylate, sodium persulfate and sodium polystyrene sulfonate into water, uniformly mixing for 60min at the rotating speed of 2000r/min, heating to 70 ℃ under the protection of nitrogen, reacting for 2h, and cooling to 30 ℃ to obtain the ACR seed emulsion.
Preparation examples 6-10 and comparative preparation examples 1,2 provide ACR-based impact modifiers and methods of preparing the same.
Preparation example 6
The ACR impact modifier comprises the following raw materials: 10g of ACR seed emulsion, 20g of ethyl acrylate, 0.6g of allyl methacrylate, 1g of diallyl phthalate, 0.5g of sophorolipid, 0.05g of cumene hydroperoxide, 5g of nano silicon dioxide, 1g of organic bentonite, 0.01g of demulsifier X-75 and 40g of water;
wherein, ACR seed emulsion is prepared by preparation example 1;
an ACR-based impact modifier prepared by the process of:
S11, adding ACR seed emulsion, ethyl acrylate, diallyl phthalate, sophorolipid and cumene hydroperoxide into water, performing ultrasonic dispersion for 40min, heating to 50 ℃ under the protection of nitrogen, and performing heat preservation reaction for 3h to obtain ACR emulsion;
S12, adding allyl methacrylate, nano silicon dioxide and organic bentonite into the ACR emulsion obtained in the step S11, fully reacting for 2 hours at 75 ℃, adding a demulsifier X-75, washing with water and drying to obtain the ACR impact modifier.
Preparation example 7
The ACR impact modifier comprises the following raw materials: 12g of ACR seed emulsion, 22g of ethyl acrylate, 0.7g of allyl methacrylate, 1.2g of diallyl phthalate, 0.6g of sophorolipid, 0.06g of cumene hydroperoxide, 5.5g of nano silicon dioxide, 1.5g of organic bentonite, 0.02g of demulsifier X-75 and 45g of water;
wherein, ACR seed emulsion is prepared by preparation example 2;
an ACR-based impact modifier prepared by the process of:
S11, adding ACR seed emulsion, ethyl acrylate, diallyl phthalate, sophorolipid and cumene hydroperoxide into water, performing ultrasonic dispersion for 45min, heating to 55 ℃ under the protection of nitrogen, and performing heat preservation reaction for 2.5h to obtain ACR emulsion;
S12, adding allyl methacrylate, nano silicon dioxide and organic bentonite into the ACR emulsion obtained in the step S11, fully reacting for 1.8 hours at 78 ℃, adding a demulsifier X-75, washing with water, and drying to obtain the ACR impact modifier.
Preparation example 8
The ACR impact modifier comprises the following raw materials: 15g of ACR seed emulsion, 25g of ethyl acrylate, 0.8g of allyl methacrylate, 1.5g of diallyl phthalate, 0.7g of sophorolipid, 0.07g of cumene hydroperoxide, 6g of nano silicon dioxide, 2g of organic bentonite, 0.03g of demulsifier X-75 and 50g of water;
wherein, ACR seed emulsion is prepared by preparation example 3;
an ACR-based impact modifier prepared by the process of:
s11, adding ACR seed emulsion, ethyl acrylate, diallyl phthalate, sophorolipid and cumene hydroperoxide into water, performing ultrasonic dispersion for 50min, heating to 60 ℃ under the protection of nitrogen, and performing heat preservation reaction for 2h to obtain ACR emulsion;
s12, adding allyl methacrylate, nano silicon dioxide and organic bentonite into the ACR emulsion obtained in the step S11, fully reacting for 1.5 hours at 80 ℃, adding a demulsifier X-75, washing with water, and drying to obtain the ACR impact modifier.
Preparation example 9
The ACR impact modifier comprises the following raw materials: 18g of ACR seed emulsion, 28g of ethyl acrylate, 0.9g of allyl methacrylate, 1.8g of diallyl phthalate, 0.8g of sophorolipid, 0.09g of cumene hydroperoxide, 6.5g of nano silicon dioxide, 2.5g of organic bentonite, 0.04g of demulsifier X-75 and 55g of water;
Wherein, ACR seed emulsion is prepared by preparation example 4;
an ACR-based impact modifier prepared by the process of:
S11, adding ACR seed emulsion, ethyl acrylate, diallyl phthalate, sophorolipid and cumene hydroperoxide into water, performing ultrasonic dispersion for 55min, heating to 65 ℃ under the protection of nitrogen, and performing heat preservation reaction for 1.5h to obtain ACR emulsion;
S12, adding allyl methacrylate, nano silicon dioxide and organic bentonite into the ACR emulsion obtained in the step S11, fully reacting for 1.2 hours at 82 ℃, adding a demulsifier X-75, washing with water, and drying to obtain the ACR impact modifier.
Preparation example 10
The ACR impact modifier comprises the following raw materials: 20g of ACR seed emulsion, 30g of ethyl acrylate, 1g of allyl methacrylate, 2g of diallyl phthalate, 0.9g of sophorolipid, 0.1g of cumene hydroperoxide, 7g of nano silicon dioxide, 3g of organic bentonite, 0.05g of demulsifier X-75 and 60g of water;
wherein, ACR seed emulsion is prepared by preparation example 5;
an ACR-based impact modifier prepared by the process of:
S11, adding ACR seed emulsion, ethyl acrylate, diallyl phthalate, sophorolipid and cumene hydroperoxide into water, performing ultrasonic dispersion for 60min, heating to 70 ℃ under the protection of nitrogen, and performing heat preservation reaction for 1h to obtain ACR emulsion;
S12, adding allyl methacrylate, nano silicon dioxide and organic bentonite into the ACR emulsion obtained in the step S11, fully reacting for 1h at 85 ℃, adding a demulsifier X-75, washing with water, and drying to obtain the ACR impact modifier.
Comparative preparation example 1
Comparative preparation 1, differs from preparation 6 in that: no nano silica was added.
Comparative preparation example 2
Comparative preparation 2 differs from preparation 6 in that: no organobentonite is added.
Preparation examples 11-15 and comparative preparation examples 3-5 provided PVC resins pretreated.
PREPARATION EXAMPLE 11
The PVC resin is pretreated:
firstly, treating 100g of PVC resin with plasma at 50 ℃, uniformly mixing the PVC resin with 400g of solvent, standing and swelling for 1h, evaporating the solvent at 110 ℃, and then, keeping warm, standing and ageing for 3h to obtain an ageing material; drying and crushing the aged material to obtain pretreated PVC resin;
Wherein the solvent is prepared by mixing diethyl ether and tetrahydrofuran in a mass ratio of 3:5.
Preparation example 12
The PVC resin is pretreated:
firstly, treating 100g of PVC resin with plasma at 55 ℃, uniformly mixing the PVC resin with 450g of solvent, standing and swelling for 1.2 hours, evaporating the solvent at 112 ℃, and then carrying out heat preservation, standing and ageing for 3.2 hours to obtain an ageing material; drying and crushing the aged material to obtain pretreated PVC resin;
Wherein the solvent is prepared by mixing diethyl ether and tetrahydrofuran in a mass ratio of 4:5.
Preparation example 13
The PVC resin is pretreated:
firstly, treating 100g of PVC resin with plasma at 60 ℃, uniformly mixing the PVC resin with 500g of solvent, standing and swelling for 1.5h, evaporating the solvent at 115 ℃, and then keeping the temperature, standing and ageing for 3.5h to obtain an ageing material; drying and crushing the aged material to obtain pretreated PVC resin;
wherein the solvent is prepared by mixing diethyl ether and tetrahydrofuran in a mass ratio of 1:1.
PREPARATION EXAMPLE 14
The PVC resin is pretreated:
Firstly, treating 100g of PVC resin with plasma at 65 ℃, uniformly mixing the PVC resin with 550g of solvent, standing and swelling for 1.8 hours, evaporating the solvent at 118 ℃, and then, keeping warm, standing and ageing for 3.8 hours to obtain an ageing material; drying and crushing the aged material to obtain pretreated PVC resin;
wherein the solvent is prepared by mixing diethyl ether and tetrahydrofuran in a mass ratio of 6:5.
Preparation example 15
The PVC resin is pretreated:
Firstly, treating 100g of PVC resin with plasma at 70 ℃, uniformly mixing the PVC resin with 600g of solvent, standing and swelling for 2 hours, evaporating the solvent at 120 ℃, and then, keeping warm, standing and ageing for 4 hours to obtain an ageing material; drying and crushing the aged material to obtain pretreated PVC resin;
wherein the solvent is prepared by mixing diethyl ether and tetrahydrofuran in a mass ratio of 7:5.
Comparative preparation example 3
Comparative preparation 3 differs from preparation 11 in that: the solvent is only diethyl ether.
Comparative preparation example 4
Comparative preparation 4 differs from preparation 11 in that: the solvent is tetrahydrofuran only.
Comparative preparation example 5
Comparative preparation 5 differs from preparation 11 in that: 100g of PVC resin was treated with plasma at 50℃to obtain a pretreated PVC resin.
Comparative preparation example 6
Comparative preparation 6, which differs from preparation 11 in that: uniformly mixing 100g of PVC resin with 400g of solvent, standing and swelling for 1h, evaporating the solvent at 110 ℃, and then preserving heat and standing and ageing for 3h to obtain an ageing material; drying and crushing the aged material to obtain pretreated PVC resin; wherein the solvent is prepared by mixing diethyl ether and tetrahydrofuran in a mass ratio of 3:5.
Examples 1-13 provide high strength plastic acoustic tubes and processes for their production.
Example 1
The high-strength plastic sound tube comprises the following raw materials: 100g of PVC resin, 2g of ACR impact modifier, 0.6g of organotin stabilizer, 5g of MBS modifier, 0.1g of oxidized polyethylene wax, 0.2g of calcium stearate, 0.3g of polyethylene wax, 3g of nano calcium carbonate and 0.2g of processing modifier;
Wherein, PVC resin is pretreated by preparation example 11; ACR-based impact modifiers were prepared from preparation 6; the organotin stabilizer is methyl tin mercaptide; MBS modifier is obtained by mixing MBS M-41 and MBS B-521 in a mass ratio of 5:4; the processing modifier is P-551J;
The production process of the high-strength plastic sound tube comprises the following steps:
S1, according to a formula, taking PVC resin, an organotin stabilizer, an ACR impact modifier, an MBS modifier, oxidized polyethylene wax, calcium stearate, polyethylene wax, nano calcium carbonate and a processing modifier, stirring for 30min at a rotating speed of 600r/min, and uniformly mixing to obtain a mixed material; plasticizing and extruding the mixture, wherein the extruding temperature is 170 ℃, and the extruding screw speed is 10r/min to obtain a tube blank;
S2, firstly, performing two-way stretching on the tube blank, performing first-way stretching at 100 ℃ with a radial stretching ratio of 1.5, performing vacuum setting, and cooling to 50 ℃; heating to 90 ℃ for the second time, carrying out the second biaxial stretching with the circumferential stretching ratio of 1, carrying out vacuum shaping, and cooling to 20 ℃ to obtain a crude product; and (3) carrying out surface treatment and cutting on the crude product to obtain the high-strength plastic sound tube.
Example 2
The high-strength plastic sound tube comprises the following raw materials: 100g of PVC resin, 2.5g of ACR impact modifier, 0.8g of organotin stabilizer, 5.5g of MBS modifier, 0.15g of oxidized polyethylene wax, 0.25g of calcium stearate, 0.4g of polyethylene wax, 4g of nano calcium carbonate and 0.25g of processing modifier;
wherein, PVC resin is pretreated by preparation example 12; ACR-based impact modifiers were prepared from preparation 7; the organotin stabilizer is methyl tin mercaptide; MBS modifier is prepared by mixing MBS M-41 and MBS B-521 in a mass ratio of 1:1; the processing modifier is P-551J;
The production process of the high-strength plastic sound tube comprises the following steps:
s1, according to a formula, taking PVC resin, an organotin stabilizer, an ACR impact modifier, an MBS modifier, oxidized polyethylene wax, calcium stearate, polyethylene wax, nano calcium carbonate and a processing modifier, stirring for 25min at a rotating speed of 700r/min, and uniformly mixing to obtain a mixed material; plasticizing and extruding the mixture, wherein the extruding temperature is 180 ℃, and the extruding screw speed is 9.5r/min to obtain a tube blank;
S2, firstly, performing two-way stretching on the tube blank, performing first-way stretching at 110 ℃ with a circumferential stretching ratio of 1.8, performing vacuum setting, and cooling to 55 ℃; heating to 90 ℃ for the second time, carrying out the second biaxial stretching with the circumferential stretching ratio of 1.2, carrying out vacuum shaping, and cooling to 25 ℃ to obtain a crude product; and (3) carrying out surface treatment and cutting on the crude product to obtain the high-strength plastic sound tube.
Example 3
The high-strength plastic sound tube comprises the following raw materials: 100g of PVC resin, 3g of ACR impact modifier, 1g of organotin stabilizer, 6g of MBS modified, 0.2g of oxidized polyethylene wax, 0.4g of calcium stearate, 0.5g of polyethylene wax, 6g of nano calcium carbonate and 0.4g of processing modifier;
wherein, PVC resin is pretreated by a preparation example 13; ACR-based impact modifiers were prepared from preparation 8; the organotin stabilizer is dibutyl tin maleate; MBS modifier is prepared by mixing MBS M-41 and MBS B-521 in a mass ratio of 5:6; the processing modifier is P-551;
The production process of the high-strength plastic sound tube comprises the following steps:
S1, according to a formula, taking PVC resin, an organotin stabilizer, an ACR impact modifier, an MBS modifier, oxidized polyethylene wax, calcium stearate, polyethylene wax, nano calcium carbonate and a processing modifier, stirring for 20min at a rotating speed of 800r/min, and uniformly mixing to obtain a mixed material; plasticizing and extruding the mixture, wherein the extruding temperature is 185 ℃, and the extruding screw speed is 9/min, so as to obtain a tube blank;
s2, firstly, performing two-way stretching on the tube blank, performing the first two-way stretching with the radial stretching ratio of 2 at 120 ℃, performing vacuum setting, and cooling to 60 ℃; heating to 95 ℃ for the second time, carrying out the second biaxial stretching with the circumferential stretching ratio of 1.5, carrying out vacuum shaping, and cooling to 25 ℃ to obtain a crude product; and (3) carrying out surface treatment and cutting on the crude product to obtain the high-strength plastic sound tube.
Example 4
The high-strength plastic sound tube comprises the following raw materials: 100g of PVC resin, 3.5g of ACR impact modifier, 1.2g of organotin stabilizer, 7g of MBS modifier, 0.25g of oxidized polyethylene wax, 0.4g of calcium stearate, 0.5g of polyethylene wax, 7.5g of nano calcium carbonate and 0.45g of processing modifier;
Wherein, PVC resin is pretreated by preparation example 14; ACR-based impact modifiers were prepared from preparation 9; the organotin stabilizer is methyl tin mercaptide; MBS modifier is obtained by mixing MBS M-41 and MBS B-521 in a mass ratio of 5:8; the processing modifier is P-551J;
The production process of the high-strength plastic sound tube comprises the following steps:
S1, according to a formula, taking PVC resin, an organotin stabilizer, an ACR impact modifier, an MBS modifier, oxidized polyethylene wax, calcium stearate, polyethylene wax, nano calcium carbonate and a processing modifier, stirring for 15min at a rotating speed of 900r/min, and uniformly mixing to obtain a mixed material; plasticizing and extruding the mixture, wherein the extruding temperature is 190 ℃, and the extruding screw speed is 8.5r/min to obtain a tube blank;
S2, firstly, performing two-way stretching on the tube blank, performing the first two-way stretching at 130 ℃ with a radial stretching ratio of 2.8, performing vacuum setting, and cooling to 65 ℃; heating to 98 ℃ for the second time, carrying out the second biaxial stretching with the circumferential stretching ratio of 1.8, carrying out vacuum shaping, and cooling to 28 ℃ to obtain a crude product; and (3) carrying out surface treatment and cutting on the crude product to obtain the high-strength plastic sound tube.
Example 5
The high-strength plastic sound tube comprises the following raw materials: 100g of PVC resin, 4g of ACR impact modifier, 1.4g of organotin stabilizer, 8g of MBS modifier, 0.3g of oxidized polyethylene wax, 0.5g of calcium stearate, 0.7g of polyethylene wax, 8g of nano calcium carbonate and 0.5g of processing modifier;
wherein, PVC resin is pretreated by preparation example 15; ACR-based impact modifiers were prepared from preparation 10; the organotin stabilizer is methyl tin mercaptide; MBS modifier is obtained by mixing MBS M-41 and MBS B-521 in a mass ratio of 5:9; the processing modifier is P-551J;
The production process of the high-strength plastic sound tube comprises the following steps:
S1, according to a formula, taking PVC resin, an organotin stabilizer, an ACR impact modifier, an MBS modifier, oxidized polyethylene wax, calcium stearate, polyethylene wax, nano calcium carbonate and a processing modifier, stirring for 10min at a rotating speed of 1000r/min, and uniformly mixing to obtain a mixed material; plasticizing and extruding the mixture, wherein the extruding temperature is 200 ℃, and the extruding screw speed is 8r/min to obtain a tube blank;
s2, firstly performing two-way stretching on the tube blank, performing the first two-way stretching with the radial stretching ratio of 3 at 140 ℃, performing vacuum setting, and cooling to 70 ℃; heating to 100deg.C for the second time, performing biaxial stretching with circumferential stretching ratio of 2, vacuum shaping, and cooling to 30deg.C to obtain crude product; and (3) carrying out surface treatment and cutting on the crude product to obtain the high-strength plastic sound tube.
Example 6
Example 6, which differs from example 1 only in that: the organotin stabilizer is dibutyl tin maleate.
Example 7
Example 7, which differs from example 1 only in that: the organotin stabilizer is prepared by mixing methyl tin mercaptide and dibutyl tin maleate in a mass ratio of 1:1.
Example 8
Example 8, which differs from example 1 only in that: the processing modifier is JL-M01.
Example 9
Example 9, which differs from example 1 only in that: the processing modifier is JL-G01FX.
Example 10
Example 10, which differs from example 1 only in that: the processing modifier is prepared by mixing P-551J and JL-M01 in a mass ratio of 1:1.
Example 11
Example 11 differs from example 1 only in that: the processing modifier is prepared by mixing JL-M01 and JL-G01FX in a mass ratio of 1:1.
Example 12
Example 12, which differs from example 1 only in that: the processing modifier is prepared by mixing P-551J and JL-G01FX in a mass ratio of 1:1.
Example 13
Example 13, which differs from example 1 only in that: the processing modifier is prepared by mixing P-551, JJL-M01 and JL-M01 in a mass ratio of 1:1.
To verify the performance of the high strength plastic acoustic tubes of the present application, applicants set comparative examples 1-14, wherein: comparative example 1
Comparative example 1, which differs from example 1 only in that: ACR-based impact modifiers were prepared from comparative preparation 1.
Comparative example 2
Comparative example 2, which differs from example 1 only in that: ACR-based impact modifiers were prepared from comparative preparation 2.
Comparative example 3
Comparative example 3, which differs from example 1 only in that: the ACR-based impact modifier is ACR401.
Comparative example 4
Comparative example 4, which differs from example 1 only in that: the ACR type impact modifier is ACR PA-40.
Comparative example 5
Comparative example 5, which differs from example 1 only in that: the PVC resin was pretreated by comparative preparation 3.
Comparative example 6
Comparative example 6, which differs from example 1 only in that: the PVC resin was pretreated by comparative preparation 4.
Comparative example 7
Comparative example 7, which differs from example 1 only in that: the PVC resin was pretreated by means of preparation example 5.
Comparative example 8
Comparative example 8, which differs from example 1 only in that: the PVC resin was pretreated by means of preparation example 6.
Comparative example 9
Comparative example 9, which differs from example 1 only in that: the PVC resin was not pretreated.
Comparative example 10
Comparative example 10, which differs from example 1 only in that: the organotin stabilizer is dimethyltin.
Comparative example 11
Comparative example 11, which is identical to example 1, differs in that: the MBS modifier is MBS M-41 only.
Comparative example 12
Comparative example 12, which is identical to example 1, differs in that: the MBS-type modifier is MBS B-521 only.
Comparative example 13
Comparative example 13, which is identical to example 1, differs in that: the MBS-type modifier is MBS M-732 only.
Comparative example 14
Comparative example 14, which is identical to example 1, differs in that: the processing modifier is JL-G01.
The main properties of the high-strength plastic acoustic tubes obtained in examples 1 to 13 and comparative examples 1 to 14 were examined, respectively, to obtain the following result parameters, specifically shown in Table 1:
Part 2 of the measurement of the tensile Properties of thermoplastic pipes with reference to national Standard GB/T8804.2-2003: the tensile strength of the plastic acoustic tube is tested by hard polyvinyl chloride (PVC-U), chlorinated polyvinyl chloride (PVC-C) and high impact polyvinyl chloride (PVC-HI) tubing;
determination of impact Strength of thermoplastic tubing simply-supported Beam part 1 with reference to national Standard GB/T18743.1-2022: the general test method is used for testing the impact strength of the plastic acoustic tube;
Table 1:
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as can be seen from the data shown in table 1: the plastic acoustic pipes prepared in the embodiments 1 to 13 of the application have the comprehensive performance superior to that of the plastic acoustic pipes prepared in the comparative examples 1 to 14, have obvious tensile property and excellent impact resistance, and have wide market prospect.
From example 1 and comparative examples 1 and 2, it is understood that: the ACR-based impact modifier of example 1 was prepared from preparation example 6, to which nano silica and organobentonite were added, and the tensile strength and impact strength of the plastic sound tube prepared in example 1 were greater than those of comparative examples 1 and 2.
As can be seen from example 1 and comparative examples 3 and 4: the ACR-based impact modifier of example 1 was prepared in preparation example 6, and the tensile strength and impact strength of the plastic acoustic tube prepared in example 1 were significantly enhanced as compared with those of comparative examples 3 and 4.
As can be seen from example 1 and comparative examples 5 and 6: the PVC resin of example 1 was pretreated in preparation 11 using a solvent comprising diethyl ether and tetrahydrofuran, and the plastic acoustic tube prepared in example 1 was more excellent in performance than those prepared in comparative examples 5 and 6.
From example 1 and comparative examples 7 to 9, it is understood that: the PVC resin of example 1 was pretreated by preparation 11, plasma treated and then swollen with solvent, and the mechanical properties of the plastic acoustic tube prepared in example 1 were better than those of comparative examples 7 to 9.
From examples 1, 6, 7 and comparative example 10, it can be seen that: the organotin stabilizers of examples 1, 6 and 7 are methyl tin mercaptide and/or dibutyl tin maleate, and the tensile properties and impact resistance of the plastic sound tube prepared in comparative example 10 are inferior to those of examples 1, 6 and 7, compared with comparative example 10.
From example 1 and comparative examples 11 to 13, the MBS-based modifier in example 1 was obtained by mixing MBS B-521 and MBS M-41, and the impact resistance of the plastic sound tube obtained in example 1 was significantly improved as compared with comparative examples 11 to 13.
The plastic acoustic pipes prepared in examples 1, 8-13 and comparative example 14 have better overall performance than comparative example 14, compared with comparative example 14, in which the processing modifier in examples 1, 8-13 is at least one of P-551J, JL-M01 and JL-G01 FX.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.

Claims (3)

1. The high-strength plastic sound tube is characterized by comprising the following raw materials in parts by weight: 100 parts of PVC resin, 2-4 parts of ACR impact modifier, 0.6-1.4 parts of organotin stabilizer, 5-8 parts of MBS modifier, 0.1-0.3 part of oxidized polyethylene wax, 0.2-0.5 part of calcium stearate, 0.3-0.7 part of polyethylene wax, 3-8 parts of nano calcium carbonate and 0.2-0.5 part of processing modifier;
The ACR impact modifier comprises the following raw materials in parts by weight: 10-20 parts of ACR seed emulsion, 20-30 parts of ethyl acrylate, 0.6-1 part of allyl methacrylate, 1-2 parts of diallyl phthalate, 0.5-0.9 part of sophorolipid, 0.05-0.1 part of cumene hydroperoxide, 5-7 parts of nano silicon dioxide, 1-3 parts of organic bentonite, 0.01-0.05 part of demulsifier and 40-60 parts of water;
the ACR type impact modifier is prepared by the following method:
S11, adding ACR seed emulsion, ethyl acrylate, diallyl phthalate, sophorolipid and cumene hydroperoxide into water, performing ultrasonic dispersion for 40-60min, heating to 50-70 ℃ under the protection of nitrogen, and performing heat preservation reaction for 1-3h to obtain ACR emulsion;
S12, adding allyl methacrylate, nano silicon dioxide and organic bentonite into the ACR emulsion obtained in the step S11, fully reacting for 1-2 hours at 75-85 ℃, adding a demulsifier, washing with water and drying to obtain the ACR impact modifier;
the ACR seed emulsion comprises the following raw materials in parts by weight: 30-40 parts of butyl acrylate, 6-10 parts of neopentyl glycol diacrylate, 0.5-0.9 part of sodium polystyrene sulfonate, 0.02-0.08 part of sodium persulfate and 30-40 parts of water;
the ACR seed emulsion is prepared by the following method:
Adding butyl acrylate, neopentyl glycol diacrylate, sodium persulfate and sodium polystyrene sulfonate into water, uniformly mixing for 30-60min at the rotating speed of 2000-3000r/min, heating to 40-70 ℃ under the protection of nitrogen, reacting for 2-4h, and cooling to 20-30 ℃ to obtain ACR seed emulsion;
the PVC resin is also subjected to pretreatment:
Firstly, treating PVC resin by using plasma at 50-70 ℃, uniformly mixing the PVC resin and a solvent according to the mass ratio of 1:4-6, standing and swelling for 1-2h, evaporating the solvent at 110-120 ℃, and then, keeping warm, standing and aging for 3-4h to obtain an aged material; drying and crushing the aged material to obtain pretreated PVC resin;
the solvent is prepared by mixing diethyl ether and tetrahydrofuran in a mass ratio of 3-7:5;
The MBS modifier is prepared by mixing MBS M-41 and MBS B-521 in a mass ratio of 5:4-9;
the organic tin stabilizer is methyl tin mercaptide and/or dibutyl tin maleate;
the processing modifier is at least one of P-551J, JL-M01 and JL-G01 FX.
2. A process for producing a high strength plastic acoustic tube according to claim 1, comprising the steps of:
S1, uniformly mixing PVC resin, an organotin stabilizer, an ACR impact modifier, an MBS modifier, oxidized polyethylene wax, calcium stearate, polyethylene wax, nano calcium carbonate and a processing modifier according to a formula to obtain a mixed material; plasticizing and extruding the mixture to obtain a tube blank;
s2, performing two-way stretching on the tube blank to obtain a crude product; and (3) carrying out surface treatment and cutting on the crude product to obtain the high-strength plastic sound tube.
3. The process for producing a high-strength plastic sound tube according to claim 2, wherein the specific operation of two biaxial stretching in step S2 is as follows: performing first biaxial stretching at 100-140deg.C with radial stretching ratio of 1.5-3, vacuum shaping, and cooling to 50-70deg.C; and heating to 90-100 ℃ for the second time, carrying out two-way stretching for the second time according to the circumferential stretching ratio of 1-2, carrying out vacuum shaping, and cooling to 20-30 ℃.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20010026353A (en) * 1999-09-06 2001-04-06 신진욱 Unplasticised Polyvinyl- chloride with Impact modifier
CN107540975A (en) * 2016-06-29 2018-01-05 中国石油化工股份有限公司 A kind of high rush-resistant polyvinyl chloride water-feeding pipes and preparation method thereof
CN109370107A (en) * 2018-10-23 2019-02-22 上海上塑控股(集团)有限公司 A kind of high shock resistance type PVC-U pipe fitting and preparation method thereof
CN109438872A (en) * 2018-10-25 2019-03-08 宜宾天原集团股份有限公司 A kind of high-strength and high ductility polyvinyl chloride pipe formulation and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20010026353A (en) * 1999-09-06 2001-04-06 신진욱 Unplasticised Polyvinyl- chloride with Impact modifier
CN107540975A (en) * 2016-06-29 2018-01-05 中国石油化工股份有限公司 A kind of high rush-resistant polyvinyl chloride water-feeding pipes and preparation method thereof
CN109370107A (en) * 2018-10-23 2019-02-22 上海上塑控股(集团)有限公司 A kind of high shock resistance type PVC-U pipe fitting and preparation method thereof
CN109438872A (en) * 2018-10-25 2019-03-08 宜宾天原集团股份有限公司 A kind of high-strength and high ductility polyvinyl chloride pipe formulation and preparation method thereof

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