CN101817951B

CN101817951B - Waterproof roll material with improved ageing resistance and preparation method thereof

Info

Publication number: CN101817951B
Application number: CN2010101676511A
Authority: CN
Inventors: 赵健
Original assignee: Individual
Current assignee: Shanxi Sifang Hengtai Waterproof Materials Co ltd
Priority date: 2010-05-11
Filing date: 2010-05-11
Publication date: 2012-02-08
Anticipated expiration: 2030-05-11
Also published as: CN101817951A

Abstract

The invention relates to a waterproof roll material, in particular to a chlorinated polyethylene waterproof roll material with improved ageing resistance and a preparation method thereof, which solves the problems that the conventional waterproof roll material cannot completely meet performance indexes of the products and a formula has too high cost. The waterproof roll material is prepared from ETHYLENE/OCTENE COPOLYMER, chlorinated polyethylene, linear high pressure polyethylene, a reinforcing filler, a softening plasticizer, a phenol antioxidant, a thermal stabilizer, a lubricating agent and a light stabilizer. The preparation method comprises the following steps of: mixing and stirring various raw materials; granulating by adopting a plastic mixing mill, a two roll machine and a granulator in turn; extruding the granules by using a single screw extrusion machine and moulding by using a die; and rolling and pressing the moulded material by using a three-roller cooling embossing press into the waterproof roll material. The waterproof roll material not only maintains unique flexibility, elongation and rebound elasticity of rubber, but also maintains high breaking strength of LLDPE, and has good flexibility, flatness and evenness integrally, performance indexes exceeding national standard and related standard of Ministry of Railways, good ageing resistance, physical performance and processability, and low production cost.

Description

A kind of waterproof roll that improves ageing-resistant performance and preparation method thereof

Technical field

The present invention relates to a kind of waterproof roll, be specially a kind of improvement ageing-resistant performance, physicals and processing characteristics waterproof roll and preparation method thereof.

Background technology

At present each manufacturer special-purpose N class (no composite bed coiled material) of bridge, L class (two-sided compound nonwoven cloth) type waterproof roll of producing adopts high-pressure polyethylene or linear low density polyethylene to come modified chlorinated polyethylene to do the waterproof roll matrix basically.Though the prescription of each manufacturer, technology difference all exist very big defective; (1) if be the main body with high-pressure polyethylene or linear low density polyethylene, though each item mechanical property can reach the related standards of the Ministry of Railways,, the pliability of product, planeness, rebound resilience do not reach the requirement of construction far away.Because bridge construction special-purpose water-proof coiled material has certain particular requirement to its pliability, planeness and rebound resilience, otherwise just be difficult to make the comprehensive cement based bonding of waterproof roll to be one with bridge floor.A lot of producers are therefore defective and can't normally use and returned goods; (2) if be the main body with chlorinatedpolyethylene (CPE); The pliability of product, planeness, rebound resilience are all relatively good; But its mechanical performance index then differs greatly, particularly breaking tenacity can only be about 90N/cm/1.5mm (related standards of the Ministry of Railways is >=160N/cm/1.5mm-1.8mm); (3) if these two kinds of materials of high-pressure polyethylene and chlorinatedpolyethylene are homogeneous phase, equity, its mechanical property and pliability, planeness, rebound resilience are then all defective.In addition, also have part producer to use TPR SBS or thermoplastic elastomer TPE etc. to be material of main part at present, though various performance index can both reach requirement, formulation cost is too high, can not adapt to the running of present market economy.Do not see the report of ethene-octene copolymer (POE) successful application up to now as yet at bridge construction special-purpose water-proof coiled material.

Summary of the invention

The present invention adopts high-pressure polyethylene to come modified chlorinated polyethylene to do the waterproof roll matrix in order to solve the special-purpose two types of waterproof rolls of existing bridge construction basically, can't satisfy product each item performance index fully.If adopting TPR SBS or thermoplastic elastomer TPE is material of main part, cause the too high problem of formulation cost, a kind of modified chlorinated polyethylene waterproof roll and preparation method thereof is provided.

The present invention adopts following technical scheme to realize: a kind of chlorinated polyethylene waterproof roll that improves ageing-resistant performance, process by the raw material of following parts by weight: 80～100 parts of ethene-octene copolymers, 80～100 parts of chlorinatedpolyethylenees; 160～200 parts of linear low density polyethylenes are filled 80～200 parts of tougheners, 75～90 parts in softening softening agent; 2～4 parts of phenolic antioxidants; 2～4 parts of thermo-stabilizers, 2～4 parts of lubricants, 1.5～2.5 parts of photostabilizers; Described phenolic antioxidant is that 50% phenols primary antioxidant 1010 and 50% phenols auxiliary antioxidant 168 are processed by weight ratio, and described thermo-stabilizer is that 50% dibasic lead phosphite and 50% lead sulfate tribasic are processed by weight ratio.

Described filling toughener is treated carbonates or colloid lime carbonate; Described softening softening agent is any one in DOP, clorafin, imitative hydrogen oil or the NO; Described lubricant is Triple Pressed Stearic Acid or particle paraffin; Described photostabilizer is UV light absorber UV327 or UV531; Octene content is 30-50wt% in said ethene-octene copolymer, and cl content is 25-45wt% in the chlorinatedpolyethylene.。

In the above-mentioned prescription; Ethene-octene copolymer (POE) is that U.S. DOW chemical company is the thermoplastic elastomer of narrow relative molecular mass of having of catalyzer and short-chain branch distribution uniformly with the metallocene; This elastomeric salient features that has a rubbery is very outstanding, and the performance index aspect a lot of have surpassed common elastomerics.Why POE has excellent performance, can realize extruding at a high speed relevant with following characteristics: flexible chain coiled structure of (1) octene and crystalline ethylene chain make it have excellent toughness and have good processibility again as the physical crosslinking point; (2) relative molecular mass narrowly distributing, good with compatible polyolefin property, have preferable flowability; (3) do not have unsaturated double-bond, excellent weather resistance and hard is in other elastomerics; (4) stronger shearing sensibility and melt strength can be realized extruding at a high speed, improves output; (5) good flowability can be improved the dispersion effect of stopping composition, also can improve the weld mark strength of goods simultaneously.The singularity of POE molecular structure has been given its excellent mechanical property, rheological property and anti-ultraviolet property.Ethene-octene copolymer (POE) is to have combined rubber and a kind of material of plastics advantage; Its plastics at high temperature are can mobile mutually; Then play the effect of physical crosslinking point at normal temperatures, this physical crosslinking is hot reversible, so it both can use the working method moulding of thermoplastics; It has the elasticity of rubber again in awide temperature range, the present invention first with ethene-octene copolymer (POE) successful application on bridge construction special-purpose water-proof coiled material.

Chlorinatedpolyethylene (CPE) is the chloride polyolefine of being processed through chlorination by Vilaterm; It is the armorphous chloride saturated elastomerics of a kind of line style; Difference according to chlorinity can be divided into soft plastic (chlorinity is less than 25%), elastomerics (chlorinity 25%～45%) and rigid plastics (chlorinity 45%～70%), because the introducing of chlorine atom makes primary structure be prone to cause that the factor of chemical degradation and thermal destruction disappears; Thereby make it have good weathering resistance, flame resistivity and resistance to low temperature; The present invention quotes chlorinatedpolyethylene in design, except above-mentioned factor, also have the adhesion problem that important factor is exactly N class waterproof roll and cement matrix sticker; Because chlorinatedpolyethylene is a kind of polar macromolecular material that has; Superior with the adhesive property of common bond, and the adhesive property of POE, LLDPE and common bond is poor, is difficult to bonding.Prove that through test of many times the present invention preferably is advisable at 35% chlorinatedpolyethylene with chlorinity.

Because above-mentioned two type of elastomeric bodies add certain tenderizer, its tensile strength is had a greatly reduced quality do not reach the design requirements of product far away, even add suitable reinforcing filler; Though intensity has some improvement, with the design requirements of waterproof roll a certain distance is arranged still, and elongation can descend by straight line also; In order both to reach the design requirements of product performance index, consider the formulation cost of product again, the applicant is through test of many times and summary of experience; On prescription, added linear low density polyethylene (LLDPE) as the plastics phase; Under the little situation of elongation loss, its tensile strength is greatly improved, the fracture tensile strength >=18MPa of N class waterproof roll, tensile yield >=900% through test; Fracture tensile strength >=the 200N/cm/1.5mm of the two-sided compound nonwoven cloth waterproof coiled material of L class; Tensile yield >=800%, all other indexs are all above the related standards of the national standard and the Ministry of Railways, and the component design cost of product also significantly descends.

For the further prescription of optimizing this product, the index of enhancing product performance, the present invention has also added following raw material, and the effect of filling toughener is the intensity of increase product partly and the formulation cost of reduction product; The main effect of softening softening agent is the flexibility that increases product; The main effect of phenolic antioxidant is to improve product heat resistanceheat resistant, ageing resistance in use, prolongs the work-ing life of waterproof roll; The effect of thermo-stabilizer mainly is the thermolysis that prevents or stop chlorinatedpolyethylene in the course of processing, to cause owing to high temperature; The main effect of lubricant is to prevent superpolymer in the process of converted products, and the high temperature that excessively produces owing to friction decomposes superpolymer; The main effect of photostabilizer is to prevent owing to the width of cloth of light is penetrated the superpolymer decomposition that causes.

A kind of method for preparing the chlorinated polyethylene waterproof roll that improves ageing-resistant performance may further comprise the steps:

(1) batching:, stir under the normal temperature with various raw material proportional mixing; (2) granulation: drop into the closed plastics processing mill to the compound that stirs; The temperature of closed plastics processing mill is controlled at 150～170 ℃; Banburying discharging after 10～15 minutes; Directly get into twin-roll machine, the roller temperature of twin-roll machine is controlled at 140～150 ℃, roll spacing slice when being set to 3.5mm～4mm, and then through the dicing machine pelletizing; (3) pellet that step (2) is obtained drops into that single screw extrusion machine is extruded and through mould molding: the machine barrel top temperature of single screw extrusion machine is that to be controlled at 30～40 rev/mins, the core temperature of single screw extrusion machine mould be 10～15 ℃ of the core temperatures that 180～220 ℃, the both sides temperature of mould are higher than mould for 180～200 ℃, screw speed; (4) molding mass that step (3) is obtained drops into the roll-in of three rollers coolings embossing machine and goes out the N class and do not have composite bed waterproof roll or the two-sided compound nonwoven cloth type of L class waterproof roll: roller temperature was that 50～70 ℃, lower roller temperature are that 40～60 ℃, upper roller temperature are 60～80 ℃ during the roller temperature of three rollers cooling embossing machine was controlled at; (5) naturally cooling, plant the limit.Above-mentioned closed plastics processing mill, twin-roll machine, dicing machine, single screw extrusion machine and three rollers cooling embossing machine are existing known device, and its structure and principle of work are that those of ordinary skill in the art knows.

The invention uses a thermoplastic rubber phase is ethylene - octene copolymer and chlorinated polyethylene, linear low density polyethylene plastic phase, and appropriate to the amount of plasticizer, filling enhancer and various auxiliary materials, the blending squeeze out of the N-type substrate, L type of bridge dedicated waterproof membrane, the production of such rubber blends waterproof membrane does not require curing process, you can use processing ordinary thermoplastic processing technology, product features are only retained the greatest unique softness of rubber and higher elongation, elasticity, but also retains a high tensile strength of LLDPE, the overall softness of the sheet, straightness, flatness is better, its performance is much than the national standard, and the Ministry of Railways of the relevant standard, the N-type waterproofing membrane made of tensile strength> 18MPa, elongation at break> 900%, L Double-sided non-woven composite waterproofing membrane tensile Strength> 200N/cm/1.5mm, elongation at break> 800%.And the present invention adopts thermoplastic elastomer, the common modification linear low density polyethylene of TPR; Not only each item performance index are superior; The more important thing is formulation cost of the present invention and use other thermoplastic elastomer or rubber phase ratio, will hang down about 1/3rd, in a word at least; Waterproof roll ageing-resistant performance, physicals and the processing characteristics that adopts prescription of the present invention and method to obtain is all better and production cost is lower, has good application prospects.

Embodiment

Embodiment 1:

A kind of chlorinated polyethylene waterproof roll that improves ageing-resistant performance, processed by the raw material of following parts by weight: octene content is 80 parts of ethene-octene copolymers of 30wt%, cl content is 80 parts of the chlorinatedpolyethylenees of 30wt%; 160 parts of linear low density polyethylenes, 80 parts of treated carbonatess, 75 parts of DOPs; 2 parts of phenolic antioxidants; 2 parts of thermo-stabilizers, 2 parts of Triple Pressed Stearic Acid, 1.5 parts of UV light absorbers (UV327); Phenolic antioxidant is that 50% phenols primary antioxidant 1010 and 50% phenols auxiliary antioxidant 168 are processed by weight ratio, and thermo-stabilizer is that 50% dibasic lead phosphite and 50% lead sulfate tribasic are processed by weight ratio.

Preparation improves the method for the chlorinated polyethylene waterproof roll of ageing-resistant performance, may further comprise the steps: (1) batching: with various raw material proportional mixing, stir under the normal temperature; (2) granulation: drop into the closed plastics processing mill to the compound that stirs; The temperature of closed plastics processing mill is controlled at 150 ℃, and banburying discharging after 10 minutes directly gets into twin-roll machine; The roller temperature of twin-roll machine is controlled at 140 ℃, slice when roll spacing is set to 3.5mm, and then through the dicing machine pelletizing; (3) pellet that step (2) is obtained drops into that single screw extrusion machine is extruded and through mould molding: the machine barrel top temperature of single screw extrusion machine is that to be controlled at 30 rev/mins, the core temperature of single screw extrusion machine mould be 10 ℃ of the core temperatures that 190 ℃, the both sides temperature of mould are higher than mould for 190 ℃, screw speed; (4) molding mass that step (3) is obtained drops into the roll-in of three rollers coolings embossing machine and goes out the N class and do not have composite bed waterproof roll or the two-sided compound nonwoven cloth type of L class waterproof roll: roller temperature was that 50 ℃, lower roller temperature are that 40 ℃, upper roller temperature are 60 ℃ during the roller temperature of three rollers cooling embossing machine was controlled at; (5) naturally cooling, plant the limit.

Embodiment 2:

A kind of chlorinated polyethylene waterproof roll that improves ageing-resistant performance, processed by the raw material of following parts by weight: octene content is 85 parts of ethene-octene copolymers of 35wt%, cl content is 90 parts of the chlorinatedpolyethylenees of 25wt%; 170 parts of linear low density polyethylenes, 120 parts in colloid lime carbonate, 80 parts of clorafins; 2.5 parts of phenolic antioxidants; 2.5 parts of thermo-stabilizers, 2.5 parts in particle paraffin, 2.0 parts of UV light absorbers (UV327); Phenolic antioxidant is that 50% phenols primary antioxidant 1010 and 50% phenols auxiliary antioxidant 168 are processed by weight ratio, and thermo-stabilizer is that 50% dibasic lead phosphite and 50% lead sulfate tribasic are processed by weight ratio.

Preparation improves the method for the chlorinated polyethylene waterproof roll of ageing-resistant performance, may further comprise the steps: (1) batching: with various raw material proportional mixing, stir under the normal temperature; (2) granulation: drop into the closed plastics processing mill to the compound that stirs; The temperature of closed plastics processing mill is controlled at 170 ℃, and banburying discharging after 15 minutes directly gets into twin-roll machine; The roller temperature of twin-roll machine is controlled at 150 ℃, slice when roll spacing is set to 4mm, and then through the dicing machine pelletizing; (3) pellet that step (2) is obtained drops into that single screw extrusion machine is extruded and through mould molding: the machine barrel top temperature of single screw extrusion machine is that to be controlled at 40 rev/mins, the core temperature of single screw extrusion machine mould be 15 ℃ of the core temperatures that 220 ℃, the both sides temperature of mould are higher than mould for 200 ℃, screw speed; (4) molding mass that step (3) is obtained drops into the roll-in of three rollers coolings embossing machine and goes out the N class and do not have composite bed waterproof roll or the two-sided compound nonwoven cloth type of L class waterproof roll: roller temperature was that 70 ℃, lower roller temperature are that 60 ℃, upper roller temperature are 80 ℃ during the roller temperature of three rollers cooling embossing machine was controlled at; (5) naturally cooling, plant the limit.

Embodiment 3:

A kind of chlorinated polyethylene waterproof roll that improves ageing-resistant performance, processed by the raw material of following parts by weight: octene content is 90 parts of ethene-octene copolymers of 40wt%, cl content is 90 parts of the chlorinatedpolyethylenees of 40wt%; 180 parts of linear low density polyethylenes, 150 parts of treated carbonatess, 85 parts of imitative hydrogen oil; 3 parts of phenolic antioxidants; 3 parts of thermo-stabilizers, 3 parts in particle paraffin, 2 parts of UV light absorbers (UV531); Phenolic antioxidant is that 50% phenols primary antioxidant 1010 and 50% phenols auxiliary antioxidant 168 are processed by weight ratio, and thermo-stabilizer is that 50% dibasic lead phosphite and 50% lead sulfate tribasic are processed by weight ratio.

Preparation improves the method for the chlorinated polyethylene waterproof roll of ageing-resistant performance, may further comprise the steps: (1) batching: with various raw material proportional mixing, stir under the normal temperature; (2) granulation: drop into the closed plastics processing mill to the compound that stirs; The temperature of closed plastics processing mill is controlled at 170 ℃, and banburying discharging after 10 minutes directly gets into twin-roll machine; The roller temperature of twin-roll machine is controlled at 150 ℃, slice when roll spacing is set to 3.5mm, and then through the dicing machine pelletizing; (3) pellet that step (2) is obtained drops into that single screw extrusion machine is extruded and through mould molding: the machine barrel top temperature of single screw extrusion machine is that to be controlled at 35 rev/mins, the core temperature of single screw extrusion machine mould be 10 ℃ of the core temperatures that 200 ℃, the both sides temperature of mould are higher than mould for 185 ℃, screw speed; (4) molding mass that step (3) is obtained drops into the roll-in of three rollers coolings embossing machine and goes out the N class and do not have composite bed waterproof roll or the two-sided compound nonwoven cloth type of L class waterproof roll: roller temperature was that 55 ℃, lower roller temperature are that 50 ℃, upper roller temperature are 65 ℃ during the roller temperature of three rollers cooling embossing machine was controlled at; (5) naturally cooling, plant the limit.

Embodiment 4:

A kind of chlorinated polyethylene waterproof roll that improves ageing-resistant performance, processed by the raw material of following parts by weight: octene content is 95 parts of ethene-octene copolymers of 40wt%, cl content is 95 parts of the chlorinatedpolyethylenees of 40wt%; 190 parts of linear low density polyethylenes, 180 parts of treated carbonatess, 85 parts of NOs; 3.5 parts of phenolic antioxidants; 3.5 parts of thermo-stabilizers, 3.5 parts of Triple Pressed Stearic Acid, 2.5 parts of UV light absorbers (UV531); Phenolic antioxidant is that 50% phenols primary antioxidant 1010 and 50% phenols auxiliary antioxidant 168 are processed by weight ratio, and thermo-stabilizer is that 50% dibasic lead phosphite and 50% lead sulfate tribasic are processed by weight ratio.

Preparation improves the method for the chlorinated polyethylene waterproof roll of ageing-resistant performance, may further comprise the steps: (1) batching: with various raw material proportional mixing, stir under the normal temperature; (2) granulation: drop into the closed plastics processing mill to the compound that stirs; The temperature of closed plastics processing mill is controlled at 165 ℃; Banburying discharging after 12 minutes; Directly get into twin-roll machine, the roller temperature of twin-roll machine is controlled at 145 ℃, roll spacing slice when being set to 3.5mm～4mm, and then through the dicing machine pelletizing; (3) pellet that step (2) is obtained drops into that single screw extrusion machine is extruded and through mould molding: the machine barrel top temperature of single screw extrusion machine is that to be controlled at 38 rev/mins, the core temperature of single screw extrusion machine mould be 14 ℃ of the core temperatures that 210 ℃, the both sides temperature of mould are higher than mould for 195 ℃, screw speed; (4) molding mass that step (3) is obtained drops into the roll-in of three rollers coolings embossing machine and goes out the N class and do not have composite bed waterproof roll or the two-sided compound nonwoven cloth type of L class waterproof roll: roller temperature was that 60 ℃, lower roller temperature are that 55 ℃, upper roller temperature are 75 ℃ during the roller temperature of three rollers cooling embossing machine was controlled at; (5) naturally cooling, plant the limit.

Embodiment 5:

A kind of chlorinated polyethylene waterproof roll that improves ageing-resistant performance, processed by the raw material of following parts by weight: octene content is 100 parts of ethene-octene copolymers of 45wt%, cl content is 100 parts of the chlorinatedpolyethylenees of 25wt%; 200 parts of linear low density polyethylenes, 200 parts in colloid lime carbonate, 90 parts of clorafins; 4 parts of phenolic antioxidants; 4 parts of thermo-stabilizers, 4 parts of lubricants, 2.5 parts of UV light absorbers (UV327); Phenolic antioxidant is that 50% phenols primary antioxidant 1010 and 50% phenols auxiliary antioxidant 168 are processed by weight ratio, and thermo-stabilizer is that 50% dibasic lead phosphite and 50% lead sulfate tribasic are processed by weight ratio.

Preparation improves the method for the chlorinated polyethylene waterproof roll of ageing-resistant performance, may further comprise the steps: (1) batching: with various raw material proportional mixing, stir under the normal temperature; (2) granulation: drop into the closed plastics processing mill to the compound that stirs; The temperature of closed plastics processing mill is controlled at 155 ℃; Banburying discharging after 14 minutes; Directly get into twin-roll machine, the roller temperature of twin-roll machine is controlled at 147 ℃, roll spacing slice when being set to 3.5mm～4mm, and then through the dicing machine pelletizing; (3) pellet that step (2) is obtained drops into that single screw extrusion machine is extruded and through mould molding: the machine barrel top temperature of single screw extrusion machine is that to be controlled at 32 rev/mins, the core temperature of single screw extrusion machine mould be 12 ℃ of the core temperatures that 205 ℃, the both sides temperature of mould are higher than mould for 188 ℃, screw speed; (4) molding mass that step (3) is obtained drops into the roll-in of three rollers coolings embossing machine and goes out the N class and do not have composite bed waterproof roll or the two-sided compound nonwoven cloth type of L class waterproof roll: roller temperature was that 68 ℃, lower roller temperature are that 48 ℃, upper roller temperature are 80 ℃ during the roller temperature of three rollers cooling embossing machine was controlled at; (5) naturally cooling, plant the limit.

Claims

1. a chlorinated polyethylene waterproof roll that improves ageing-resistant performance is characterized in that being processed by the raw material of following parts by weight: 80～100 parts of ethylene-octene copolymers, 80～100 parts of chlorinatedpolyethylenees; 190～200 parts of linear low density polyethylenes are filled 80～200 parts of tougheners, 75～90 parts in softening softening agent; 2～4 parts of phenolic antioxidants; 2～4 parts of thermo-stabilizers, 2～4 parts of lubricants, 1.5～2.5 parts of photostabilizers; Described phenolic antioxidant is that 50% phenols primary antioxidant 1010 and 50% phenols auxiliary antioxidant 168 are processed by weight ratio; Described thermo-stabilizer is that 50% dibasic lead phosphite and 50% lead sulfate tribasic are processed by weight ratio; Octene content is 30-50wt% in the said ethylene-octene copolymer, and cl content is 25-45wt% in the chlorinatedpolyethylene.

2. a kind of chlorinated polyethylene waterproof roll that improves ageing-resistant performance according to claim 1 is characterized in that described filling toughener is treated carbonates or colloid lime carbonate.

3. a kind of chlorinated polyethylene waterproof roll that improves ageing-resistant performance according to claim 1 and 2 is characterized in that described softening softening agent is any one in DOP, clorafin, imitative hydrogen oil or the NO.

4. a kind of chlorinated polyethylene waterproof roll that improves ageing-resistant performance according to claim 1 and 2 is characterized in that described lubricant is Triple Pressed Stearic Acid or particle paraffin.

5. a kind of chlorinated polyethylene waterproof roll that improves ageing-resistant performance according to claim 1 and 2 is characterized in that described photostabilizer is UV light absorber UV327 or UV531.