CN109294117B

CN109294117B - Plum blossom pipe and production process thereof

Info

Publication number: CN109294117B
Application number: CN201811142636.4A
Authority: CN
Inventors: 邵小燕
Original assignee: HANGZHOU TONGYU INDUSTRY CO LTD
Current assignee: HANGZHOU TONGYU INDUSTRY CO LTD
Priority date: 2018-09-28
Filing date: 2018-09-28
Publication date: 2021-04-20
Anticipated expiration: 2038-09-28
Also published as: CN109294117A

Abstract

The invention discloses a plum blossom pipe and a production process thereof, relates to the field of high polymer materials, and particularly relates to a plum blossom pipe which solves the problem that the plum blossom pipe in the prior art is poor in impact resistance, and comprises the following components: 40-60 wt% of PVC resin, 6-18 wt% of impact modifier, 1-7 wt% of composite stabilizer, 25-35 wt% of composite filler and 2-6 wt% of assistant; the impact modifier comprises any two or more of ACR, MBS, CPE, ABS and EVA; the composite stabilizer comprises one or more of calcium stearate, zinc stearate and epoxidized soybean oil; the composite filler comprises any two of calcium carbonate, titanium dioxide, diatomite and rice hull powder; the auxiliary agents comprise a lubricant, a plasticizer, a toughening agent and paraffin. The plum blossom pipe has high impact resistance, certain tensile strength, tensile strength and stability, and has good appearance and transparency.

Description

Plum blossom pipe and production process thereof

Technical Field

The invention relates to the field of high polymer materials, in particular to a plum blossom pipe and a production process thereof.

Background

The quincunx pipe is a quincunx communication pipe which is formed by taking PVC particles as a main material and other formulas through a unique die, is also called a honeycomb pipe and has three types of five holes, seven holes and nine holes.

The PVC pipe has excellent physical properties, good corrosion resistance, chemical stability, flame resistance and the like, and is low in price. However, the PVC has strong intermolecular force, the material is deformed after the low-temperature impact force is applied, and the molecular structure is easily damaged, so that the impact resistance of the PVC pipe is poor, and particularly the low-temperature impact resistance is poor. The poor impact resistance of PVC materials limits the application of PVC resins in engineering structural members and the like to a certain extent. In order to improve the impact resistance of PVC resin, a toughening agent is added into a PVC matrix in the conventional method, and the toughening agent can reduce the acting force among PVC molecules, so that the impact strength of the PVC composite material can be improved.

In order to solve the above problems, chinese patent with application number cn201610598731.x discloses a high impact resistant PVC pipe, which is prepared from the following components in parts by weight: 100 parts of PVC resin, 5-10 parts of titanium dioxide, 0.1-0.3 part of CPE and 0.1-0.3 part of ACM. But the improvement of impact resistance of CPE products is limited; the high-impact ACR and ACM can keep certain rigidity of the product and improve the impact resistance of the product, but the requirements of high strength and high impact resistance of PVC pipes and pipe fittings can not be met by only adding CPE or ACM.

Disclosure of Invention

The invention aims to provide a plum blossom pipe which has the advantages of impact resistance, tensile strength, stability, heat resistance and the like, has good appearance and does not damage the original transparency of PVC.

The technical purpose of the invention is realized by the following technical scheme:

a plum blossom pipe comprises the following components: 40-60 wt% of PVC resin, 6-18 wt% of impact modifier, 1-7 wt% of composite stabilizer, 25-35 wt% of composite filler and 2-6 wt% of assistant;

the impact modifier comprises any two or more of ACR, MBS, CPE, ABS and EVA;

the composite stabilizer comprises one or more of calcium stearate, zinc stearate and epoxidized soybean oil;

the composite filler comprises any two of calcium carbonate, titanium dioxide, diatomite and rice hull powder;

the auxiliary agent comprises a lubricant, a plasticizer, a toughening agent and paraffin.

The PVC (polyvinyl chloride) resin is a polar non-polarCrystalline high polymer, density: 1.380kg/cm³Glass transition temperature: 87 ℃, so the thermal stability is poor, the processing is difficult, the direct use can not be realized, and the modified mixing and the addition of related auxiliary agents and fillers can be used. The impact modifier is a chemical for improving the low-temperature embrittlement of the high polymer material and endowing the high polymer material with higher toughness. PVC impact modifiers are numerous and mainly include: CPE resins, CPVC resins, ABS resins, MBS resins, EVA resins, NBR resins, ACR resins, and the like. In the invention, the impact modifier comprises any two or more of ACR, MBS, CPE, ABS and EVA; preferably, the impact modifier comprises ACR, MBS and CPE, and the ACR, MBS and CPE respectively account for 1-5 wt%, 2-6 wt% and 3-7 wt% of the total weight of the plum pipe; more preferably, 2-4 wt% of ACR, 3-5 wt% of MBS and 4-6 wt% of CPE.

ACR resin is special for PVC modification, and is a binary or multicomponent copolymer prepared by emulsion polymerization or suspension polymerization of methyl methacrylate as a main monomer, a small amount of acrylate (butyl acrylate, ethyl acrylate) and styrene; the ACR resin has excellent weather resistance, extremely high impact modification effect, good processing fluidity, outstanding color stability and heat resistance, and is suitable for being used as a PVC modifier. The MBS resin not only can toughen but also can keep the transparency of PVC to the maximum extent, and compared with other impact modifiers, the MBS resin can also greatly improve the toughness of products under the condition of the same addition amount. CPE and chlorinated polyethylene are high polymer materials prepared by chlorination substitution reaction of high-density polyethylene, are nontoxic and tasteless, have excellent weather resistance, ozone resistance, chemical resistance and aging resistance, have good oil resistance, flame retardance and coloring performance, have good compatibility with other high polymer materials, and have higher decomposition temperature. ABS is terpolymer of styrene (40-50%), butadiene (25-30%) and acrylonitrile (25-30%), is mainly used as engineering plastics and PVC impact modification, and has good low-temperature impact modification effect. EVA is a copolymer of ethylene and vinyl acetate acid, the crystallinity of polyethylene is changed by introducing vinyl acetate, and the refractive index of EVA is different from that of PVC, so that the EVA is often used together with other impact-resistant resin to improve the impact resistance of PVC.

In the invention, ACR, MBS and CPE are selected as impact modifiers of PVC, and the high-efficiency impact modifiers such as ABS and MBS have synergistic effect on the improvement of the impact resistance of PVC. Thus, the addition of small amounts of modifier to PVC results in high impact resistance and increases the flexibility of the PVC without significantly altering the mechanical properties of the compound. ACR is the best PVC weather resistance impact modifier, PVC/ACR can maintain high impact strength and appearance for a long time and good heat resistance, tensile strength, drug resistance and other properties, but can damage the original transparency of PVC, and a product formed by blending PVC/MBS has higher impact resistance, excellent transparency and appearance, and in order to overcome the defects of the two and play the advantages of the two, the two modifiers are used together to make up for the deficiencies, and then the PVC product with good transparency and weather resistance can be prepared. CPE has good compatibility with other high polymer materials, and improves the compatibility of ACR, MBS, CPE and PVC, thereby more efficiently modifying the impact resistance of PVC. The ACR, MBS and CPE are used for modifying PVC, so that the PVC plum pipe has certain properties of high impact strength, appearance, good heat resistance, tensile strength, drug resistance and the like while the impact resistance of the PVC is improved, and the original transparency of the PVC is not damaged.

The PVC composite stabilizer is a high-efficiency multifunctional high-tech product which is developed and produced by adopting a scientific molecular design principle, an advanced surface treatment technology, a special composite process and a strict quality monitoring system and integrates a heat stabilizer, an internal lubricant, an external lubricant, an antioxidant, a coupling agent, a dispersing agent and the like into a whole. The composite stabilizer comprises one or more of calcium stearate, zinc stearate and epoxidized soybean oil; preferably, the composite stabilizer comprises calcium stearate and zinc stearate, wherein the calcium stearate and the zinc stearate respectively account for 0.5-4 wt% and 0.5-3 wt% of the total weight of the plum pipe; more preferably, the calcium stearate is 1.5-3 wt% and the zinc stearate is 1-2.5 wt%.

The composite stabilizer mixed by calcium stearate and zinc stearate has good lubricity and good light and heat stabilizing effects, and is helpful for preventing coking in the processing process. The calcium stearate and the zinc stearate are fully mixed, so that the supply and storage of auxiliary materials are simple and convenient, the production and quality management are facilitated, the possibility of producing products in a dust-free manner is provided, the production condition is improved, and the environment is protected; the calcium stearate and the zinc stearate are fully mixed and interacted, so that the uniformity of mixing and dispersing of other components and resin can be improved; the calcium stearate has the acid absorption effect, can absorb HCl generated by thermal decomposition of PVC and remove HCl when CPE is heated, and prevents catalytic degradation of HCl, thereby improving the stability of PVC.

In the invention, the composite filler comprises any two of calcium carbonate, titanium dioxide, diatomite and rice husk powder; preferably, the composite filler comprises calcium carbonate and titanium dioxide, and the calcium carbonate and the titanium dioxide respectively account for 23-30 wt% and 2-5 wt% of the total weight of the plum blossom pipe; further preferably, the titanium dioxide is rutile type titanium dioxide; still further preferably, 25-28 wt% of calcium carbonate and 3-4 wt% of rutile type titanium dioxide.

The composite filler can make the rubber have bright color, large elongation, high tensile strength and good wear resistance. The calcium carbonate, the titanium dioxide, the diatomite and the rice hull powder are easy to obtain, renewable, nontoxic and harmless to the environment and people, belong to green materials and meet the requirement of green development. Calcium carbonate, commonly known as: limestone, stone powder, marble and the like, wherein the calcium carbonate used in the invention is colloidal calcium carbonate (activated calcium carbonate) which has higher activity than common calcium carbonate, has reinforcement property, is easy to decompose in sizing materials, and can be used as a filling material of PVC, so that the PVC has bright color and luster, high elongation, high tensile strength and good wear resistance. CPE can also be used as a modified filler, has certain filling property, and the impact resistance and the stability of PVC can be improved by using activated calcium carbonate as a filling system of the CPE. Titanium dioxide (titanium dioxide) is an important white pigment, and has superior whiteness, tinting strength, covering power, weather resistance, heat resistance and chemical stability compared with other white pigments.

The diatomite and the rice hull powder play a role in a physical cross-linking point in the composite filler, the ACR can improve the impact resistance of PVC and play a role in processing aids, the ACR can reduce the plasticizing time of the PVC, so that the diatomite and the rice hull powder in the composite filler can be fully fused with PVC resin, and can assist PVC molecular chain segments to enter pore channels of the diatomite and be anchored on the surfaces of the diatomite particles, so that the diatomite, the PVC resin, the rice hull powder and the like form an effective space network structure.

The auxiliary agent comprises a lubricant, a plasticizer, a toughening agent and paraffin. Preferably, the plasticizer is a synthetic vegetable ester; the auxiliary agent comprises 0.5-1 wt% of lubricant, 0.5-3 wt% of synthetic vegetable ester, 0.5-1 wt% of flexibilizer and 0.5-1 wt% of paraffin; further preferably 0.6-0.9 wt% of lubricant, 1.5-2 wt% of synthetic vegetable ester, 0.6-0.9 wt% of flexibilizer and 0.6-0.9 wt% of paraffin.

When modifying PVC, fillers or other additives can have an effect on the processing fluidity of PVC, reducing the processing fluidity of PVC to some extent, while the addition of certain amounts of lubricants can enhance the melt flow index.

The paraffin as a latent heat energy storage material has the advantages of large phase change latent heat, small volume change in the solid-liquid phase change process, good thermal stability, no supercooling phenomenon, no toxicity, environmental protection, low price and the like. In the invention, the polyethylene wax is preferably polyethylene wax, and the polyethylene wax refers to low molecular weight polyethylene with the molecular weight of 1500-25000 or partially oxidized low molecular weight polyethylene, and has excellent cold resistance, heat resistance, chemical resistance, wear resistance and fluidity. When a large amount of heat generated by a high-power component in the plum tube during working can be dissipated only in a limited heat dissipation area and a very short time, the phase-change material with a low melting point can quickly reach the melting point relative to the phase-change material with a high melting point, and the temperature control can be realized by fully utilizing latent heat by adding the polyethylene wax in the PVC, so that the thermal response time is relatively short; the plasticizing degree can be enhanced, the toughness and the surface smoothness of the PVC plum blossom pipe are improved, and compared with other external lubricants, the polyethylene wax can enable the PVC plum blossom pipe to have a stronger internal lubricating effect.

The plasticizer, also commonly called plasticizer, is a polymer material additive widely used in industry, and the flexibility of the plasticizer can be enhanced and the processing is easy by adding the plasticizer in plastic processing. The product has high mechanical performance, excellent gelling capacity, good saponification resistance and good resistance, and has remarkable stability at low temperature. And the synthetic plant ester is a novel environment-friendly plasticizer, is environment-friendly and pollution-free, has low product price, and has certain economic and social benefits.

The toughening agent is a substance capable of increasing the flexibility of an adhesive film layer. In the invention, an active toughening agent or an inactive toughening agent can be selected, wherein the active toughening agent is an active group which contains a molecular chain and can react with matrix resin, and can form a network structure and increase a part of flexible chains, thereby improving the shock resistance of the composite material; the inactive toughening agent is a toughening agent which is well soluble with the matrix resin but does not participate in chemical reaction.

The second purpose of the invention is to provide a production process of the plum blossom pipe, which has the advantages of simple steps and easy implementation.

a production process of a plum blossom pipe comprises the following steps:

the method comprises the following steps: weighing PVC resin, an impact modifier, a composite stabilizer, a composite filler and an auxiliary agent according to a set proportion;

step two: uniformly mixing the weighed calcium stearate and zinc stearate to obtain a composite stabilizer; uniformly mixing the weighed calcium carbonate and rutile type titanium dioxide to obtain a composite filler;

step three: uniformly mixing PVC resin, ACR, MBS, CPE, a composite stabilizer, a composite filler, a lubricant, synthetic vegetable ester, a toughening agent and paraffin to obtain a mixture;

and step four, conveying the mixture obtained in the step three to an extruder for extruding granulation, plasticizing and melting the manufactured particles, extruding and molding in a die, cooling and sizing, drawing and coiling to obtain the plum blossom tube.

Preferably, the melting temperature of the produced granules is 150-190 ℃ when the granules are plasticized and melted.

Weighing the components according to a set proportion, uniformly mixing and granulating the components, plasticizing and melting the granules, extruding, sizing, cooling and forming, drawing and coiling the granules to obtain the plum blossom pipes, and preparing the plum blossom pipes in an extrusion forming mode through granulation firstly, so that the mixing uniformity is improved to a certain extent, the performance of the prepared plum blossom pipes is more excellent, and the production process has simple steps, convenient operation and easy implementation.

In summary, compared with the prior art, the beneficial effects of the invention are as follows: the plum blossom pipe has the advantages of impact resistance, tensile strength, stability, heat resistance and the like, good appearance and no damage to the original transparency of PVC. And the production process of the plum blossom pipe has simple steps, convenient operation and easy implementation.

Detailed Description

The present invention will be described in further detail with reference to examples.

Example 1

The production process of the plum blossom pipe comprises the following steps:

the method comprises the following steps: weighing 40kg of PVC resin, 2kg of ACR, 5kg of MBS, 7kg of CPE, 4kg of calcium stearate, 2.5kg of zinc stearate, 30kg of calcium carbonate, 5kg of rutile type titanium dioxide, 1kg of lubricant, 2kg of synthetic vegetable ester, 1kg of flexibilizer and 0.5kg of paraffin.

step three: uniformly mixing weighed PVC resin, ACR, MBS, CPE, a lubricant, synthetic vegetable ester, a flexibilizer and paraffin with the composite stabilizer and the composite filler in the second step to obtain a mixture;

step four: and (3) conveying the mixture obtained in the third step into an extruder for extruding granulation, plasticizing and melting the obtained granules at 150 ℃, extruding and molding in a die, cooling and sizing, drawing, and coiling to obtain the plum blossom tube.

Example 2

The production process of the plum blossom pipe comprises the following steps:

the method comprises the following steps: 43kg of PVC resin, 4kg of ACR, 6kg of MBS, 6kg of CPE, 3kg of calcium stearate, 2kg of zinc stearate, 28kg of calcium carbonate, 2kg of rutile type titanium dioxide, 1kg of lubricant, 3kg of synthetic plant ester, 1kg of flexibilizer and 1kg of paraffin are weighed.

step four: and (3) conveying the mixture obtained in the third step into an extruder for extruding granulation, plasticizing and melting the obtained granules at 160 ℃, extruding and molding in a die, cooling and sizing, drawing, and coiling to obtain the plum blossom tube.

Example 3

The production process of the plum blossom pipe comprises the following steps:

the method comprises the following steps: 57kg of PVC resin, 3kg of ACR, 4kg of MBS, 3kg of CPE, 0.7kg of calcium stearate, 1kg of zinc stearate, 25kg of calcium carbonate, 3kg of rutile type titanium dioxide, 0.6kg of lubricant, 1.5kg of synthetic vegetable ester, 0.6kg of toughening agent and 0.6kg of paraffin are weighed.

step four: and (3) conveying the mixture obtained in the third step into an extruder for extrusion granulation, plasticizing and melting the obtained granules at 170 ℃, carrying out extrusion molding in a die, cooling and sizing, drawing, and coiling to obtain the plum blossom tube.

Example 4

The production process of the plum blossom pipe comprises the following steps:

the method comprises the following steps: 60kg of PVC resin, 4kg of ACR, 2kg of MBS, 4kg of CPE, 0.5kg of calcium stearate, 0.5kg of zinc stearate, 23kg of calcium carbonate, 3.2kg of rutile type titanium dioxide, 0.9kg of lubricant, 0.5kg of synthetic vegetable ester, 0.5kg of toughening agent and 0.9kg of paraffin are weighed.

step four: and (3) conveying the mixture obtained in the third step into an extruder for extruding granulation, plasticizing and melting the obtained granules at 180 ℃, extruding and molding in a die, cooling and sizing, drawing, and coiling to obtain the plum blossom tube.

Example 5

The production process of the plum blossom pipe comprises the following steps:

the method comprises the following steps: 50kg of PVC resin, 5kg of ACR, 3kg of MBS, 4kg of CPE, 2.2kg of calcium stearate, 3kg of zinc stearate, 26kg of calcium carbonate, 2.9kg of rutile type titanium dioxide, 0.7kg of lubricant, 1.7kg of synthetic vegetable ester, 0.7kg of toughening agent and 0.8kg of paraffin are weighed.

step four: and (3) conveying the mixture obtained in the third step into an extruder for extrusion granulation, plasticizing and melting the obtained granules at 190 ℃, carrying out extrusion molding in a die, cooling and sizing, drawing, and coiling to obtain the plum blossom tube.

Example 6

The production process of the plum blossom pipe comprises the following steps:

the method comprises the following steps: 51.2kg of PVC resin, 1kg of ACR, 4kg of MBS, 5kg of CPE, 2.5kg of calcium stearate, 2.7kg of zinc stearate, 27kg of calcium carbonate, 3.5kg of rutile type titanium dioxide, 0.8kg of lubricant, 1.8kg of synthetic vegetable ester, 0.8kg of toughening agent and 0.7kg of paraffin are weighed.

step four: and (3) conveying the mixture in the third step into an extruder for extrusion granulation, plasticizing and melting the obtained granules at 165 ℃, extruding and molding in a die, cooling and sizing, drawing, and coiling to obtain the plum blossom tube.

Example 7

The production process of the plum blossom pipe comprises the following steps:

the method comprises the following steps: 50kg of PVC resin, 1kg of ACR, 5kg of MBS, 3kg of CPE, 1.5kg of calcium stearate, 1.8kg of zinc stearate, 28kg of calcium carbonate, 4kg of rutile type titanium dioxide, 0.5kg of lubricant, 2.5kg of synthetic vegetable ester, 0.9kg of toughening agent and 0.8kg of paraffin are weighed.

step four: and (3) conveying the mixture obtained in the third step into an extruder for extrusion granulation, plasticizing and melting the obtained granules at 175 ℃, carrying out extrusion molding in a die, cooling and sizing, drawing, and coiling to obtain the plum blossom tube.

Reference group made to example 2

Comparative example 1

Comparative example 1 differs from example 2 in that no impact modifier was added to comparative example 1, and the rest remains the same as example 2.

Comparative example 2

Comparative example 2 differs from example 2 in that comparative example 2 did not include ACR and MBS, and the rest was consistent with example 2.

Comparative example 3

Comparative example 3 differs from example 2 in that no MBS or CPE was added to comparative example 3, and the rest was consistent with example 2.

And (4) testing results:

1) and observing the plum tube samples prepared in the examples 1 to 7 and the comparative examples 1 to 3, wherein the samples have the advantages of smooth surface, no bubbles, no cracks, no layering, no obvious impurities, no processing damage and the like.

2) The impact resistance of the samples prepared in examples 1 to 7 and comparative examples 1 to 3 was tested according to KGB/T16420 to 1996 standards, the samples were impacted at 0 ℃ with a D90 type hammer 1kkg1m, and the percentage of cracks was counted and recorded, with the results shown in Table 1; 3) the bending performance of the samples prepared in examples 1-7 and comparative examples 1-3 is detected according to KGB/T16419-1996 standards, and the detection results are shown in Table 1; the tensile properties of the samples prepared in examples 1-7 and comparative examples 1-3 were tested according to KGB/T16421-1996 standards, and the test results are shown in Table 1;

TABLE 1 test results record table

As can be seen from the observation of the table 1, the samples of the plum blossom tubes in the examples 1 to 7 are obviously superior to the plum blossom tubes prepared in the comparative examples 1 to 3 in tensile yield strength, external load resistance, static longitudinal recovery rate, friction factor and drop hammer impact test; and the comparative example 1 does not add ACR, MBS and CPE impact modifier, the burst of the plum tube sample in the comparative example is 90% in the drop impact test, which shows that the impact resistance of the plum tube without adding impact modifier is very poor, in the comparative examples 2 and 3, only two of the ACR, MBS and CPE impact modifiers are used, the burst of the plum tube in the comparative examples 2 and 3 is as high as 60% in the drop impact test, and it can be seen that only when the ACR, MBS and CPE impact modifier are mutually matched and act together, the burst rate of the prepared plum tube is 10%, the burst rate is lowest and the impact resistance is better.

Claims

1. A plum blossom pipe is characterized by comprising the following components: 40-60 wt% of PVC resin, 15-18 wt% of impact modifier, 1-7 wt% of composite stabilizer, 25-35 wt% of composite filler and 2-6 wt% of assistant;

the impact modifier comprises ACR, MBS and CPE, wherein the ACR, MBS and CPE respectively account for 4-5 wt%, 5-6 wt% and 6-7 wt% of the total weight of the plum pipe;

the composite stabilizer is calcium stearate and zinc stearate;

the composite filler is calcium carbonate and titanium dioxide;

the auxiliary agent comprises 0.5-1 wt% of lubricant, 0.5-3 wt% of synthetic vegetable ester, 0.5-1 wt% of toughening agent and 0.5-1 wt% of polyethylene wax.

2. The plum blossom pipe as claimed in claim 1, wherein said calcium stearate and zinc stearate are respectively 0.5 to 4wt% and 0.5 to 3wt% of the total weight of the plum blossom pipe.

3. The plum blossom pipe as claimed in claim 1, wherein said composite filler comprises calcium carbonate and titanium dioxide, said calcium carbonate and titanium dioxide respectively account for 23-30 wt% and 2-5 wt% of the total weight of the plum blossom pipe.

4. The plum blossom pipe as claimed in claim 3, wherein said titanium dioxide is rutile type titanium dioxide.

5. The plum blossom pipe as claimed in any one of claims 1 to 4, comprising the following components: 43-57 wt% of PVC resin, 4-5 wt% of ACR, 5-6 wt% of MBS, 6-7 wt% of CPE, 1.5-3 wt% of calcium stearate, 1-2.5 wt% of zinc stearate, 25-28 wt% of calcium carbonate, 3-4 wt% of rutile type titanium dioxide, 0.6-0.9 wt% of lubricant, 1.5-2 wt% of synthetic vegetable ester, 0.6-0.9 wt% of toughening agent and 0.6-0.9 wt% of polyethylene wax.

6. The production process of the plum blossom pipe as claimed in any one of claims 1 to 5, wherein the production process comprises the steps of:

step three: uniformly mixing PVC resin, ACR, MBS, CPE, a composite stabilizer, a composite filler, a lubricant, synthetic vegetable ester, a toughening agent and polyethylene wax to obtain a mixture;

7. The process for producing a plum blossom pipe as claimed in claim 6, wherein the melting temperature of said produced pellets is 150-190 ℃ when they are plasticized and melted.