CN114889264A

CN114889264A - Ultralow-temperature self-adhesive rubber asphalt polymer composite waterproof coiled material

Info

Publication number: CN114889264A
Application number: CN202210812279.8A
Authority: CN
Inventors: 王伟; 韩小翠; 郑立学; 程文青; 孙怀章
Original assignee: Weifang Yuhong Waterproof Material (Group) Co Ltd
Current assignee: Weifang Yuhong Waterproof Material (Group) Co Ltd
Priority date: 2022-07-12
Filing date: 2022-07-12
Publication date: 2022-08-12
Anticipated expiration: 2042-07-12
Also published as: CN114889264B

Abstract

The invention discloses an ultralow-temperature self-adhesive rubber asphalt polymer composite waterproof coiled material, which belongs to the technical field of waterproof materials and comprises a base course layer, an asphalt layer and an isolation layer, wherein the asphalt layer comprises the following raw materials in parts by weight: 55-65 parts of matrix asphalt, 20-28 parts of rubber oil, 15-18 parts of SBS elastomer, 2-3 parts of auxiliary agent, 12-14 parts of talcum powder and 40100.2-0.3 part of anti-aging agent. According to the invention, the auxiliary agent is added into the asphalt material, so that the heating and mixing temperature of the asphalt can be reduced by reducing the surface tension and the surface free energy of asphalt molecules; the addition of the modified asphalt can improve the flexibility of asphalt molecules, improve the low-temperature flexibility of asphalt and improve the low-temperature performance of asphalt; the addition of the auxiliary agent can also effectively improve the flammability characteristic of the asphalt and improve the flame retardant property of the asphalt material; the obtained asphalt material has excellent ultralow temperature resistance and flame retardance, and can be suitable for being used in extremely cold areas.

Description

Ultralow-temperature self-adhesive rubber asphalt polymer composite waterproof coiled material

Technical Field

The invention belongs to the technical field of waterproof materials, and particularly relates to an ultralow-temperature self-adhesive rubber asphalt polymer composite waterproof coiled material.

Background

The waterproof material is used for buildings, can prevent water from leaking and permeating, has various varieties which are divided into high, middle and low grades, is generally used as a low-grade asphalt waterproof coiled material in building engineering, has large quantity and wide range, and has poor high-temperature resistance and low-temperature resistance, flowing at the high temperature of 60 ℃ and brittle fracture and fracture at the low temperature of 0 ℃. Therefore, the SBS (styrene-butadiene-styrene polymer) modified asphalt is successfully developed in the eighties of the twentieth century to produce the waterproof coiled material, the high temperature resistance and the low temperature resistance of the asphalt waterproof coiled material can be improved, and the SBS modified asphalt waterproof coiled material has the advantages of moderate price, good waterproof effect, convenience in construction and the like, and is rapidly popularized and applied in the building waterproof industry and rapidly developed. To date, it remains one of the most important and prevalent roll products in waterproof materials.

However, the SBS modified waterproof coiled material has certain requirements on the environmental temperature, is difficult to cope with extreme high temperature or severe cold weather, when the SBS modified waterproof coiled material is in a high-temperature environment, asphalt is easy to soften due to high temperature, so that the coiled material is damaged, the waterproof effect is influenced, and when the SBS modified waterproof coiled material is in a low-temperature environment, the phenomena of temperature stress damage, bonding force reduction and the like are easy to occur due to low temperature. For example, the invention patent of China with the publication number of CN111634097A discloses an ultralow-temperature SBS waterproof coiled material, which comprises a base layer, modified asphalt layers positioned on two sides of the base layer and an isolating layer positioned on the outer side of the modified asphalt layers, wherein the modified asphalt layers comprise petroleum asphalt and tourmaline negative ion powder.

Therefore, there is still a need for an asphalt material with better low temperature performance and improved flammability characteristics of asphalt, so that the coiled material can meet the requirements of high and cold regions.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides an ultralow-temperature self-adhesive rubber asphalt polymer composite waterproof coiled material.

According to the invention, the auxiliary agent is added into the asphalt material, the prepared auxiliary agent is a block-type polymer auxiliary agent, has the property similar to that of a surfactant, is stable in chemical property of mixing and dissolving with asphalt, and can achieve the purpose of reducing the heating and mixing temperature of the asphalt by reducing the surface tension and surface free energy of asphalt molecules; in addition, the addition of the modified asphalt can improve the flexibility of asphalt molecules, improve the low-temperature flexibility of asphalt and improve the low-temperature performance of asphalt; the addition of the auxiliary agent can also effectively improve the flammability characteristic of the asphalt and improve the flame retardant property of the asphalt material; the obtained asphalt material has excellent ultralow temperature resistance, the flexibility at low temperature can reach-60 ℃ at most, and the asphalt material has flame retardant property, can be suitable for being used in extremely cold areas, and can meet higher use requirements of the asphalt material.

The purpose of the invention can be realized by the following technical scheme:

the utility model provides an ultra-low temperature self-adhesion rubber asphalt polymer composite waterproof coiled material, includes child basic unit, pitch layer and isolation layer, and the pitch layer soaks in the both sides surface of child basic unit, and the isolation layer covers on pitch layer surface.

Furthermore, the base layer of the tyre adopts long-fiber polyester non-woven fabrics impregnated by acrylic resin, so that the base layer does not absorb water and has excellent water resistance.

Further, the isolation layer is one of a PE film, a PET film or a PVC film.

Further, the asphalt layer comprises the following raw materials in parts by weight: 55-65 parts of matrix asphalt, 20-28 parts of rubber oil, 15-18 parts of SBS elastomer, 2-3 parts of auxiliary agent, 12-14 parts of talcum powder and 0.2-0.3 part of anti-aging agent 4010.

The ultra-low temperature self-adhesive rubber asphalt polymer composite waterproof coiled material is prepared by the following steps:

putting matrix asphalt and rubber oil into a stirring tank, setting the stirring temperature to be 185 ℃, sequentially adding an SBS elastomer, an auxiliary agent and an anti-aging agent 4010, stirring at the speed of 200r/min for 3.5-4h for asphalt modification, finally adding talcum powder, stirring for 1h, discharging at 185 ℃, coating an asphalt material on a base course layer which is soaked and extruded to form an asphalt layer while the asphalt material is hot, finally covering an isolation layer on the surface of the asphalt layer, and cooling, sizing and rolling to obtain the waterproof coiled material.

Further, the auxiliary agent is prepared by the following steps:

s1, adding acrylic acid and dichloromethane into a flask, adding EDCI (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and a condensing agent), uniformly stirring, adding 4-amino-1-butanol, stirring at normal temperature for reaction for 2 hours, performing rotary evaporation to remove a solvent, extracting with ethyl acetate, separating, and finally performing vacuum drying on a product at 60 ℃ for more than 3 hours to obtain an intermediate; the dosage ratio of the acrylic acid, the dichloromethane, the EDCI and the 4-amino-1-butanol is 7.2g to 300mL to 20g to 8.9 g;

-COOH on acrylic acid and-NH on 4-amino-1-butanol molecule ₂ Has high reaction activity, and can be subjected to polycondensation reaction at room temperature under the action of a condensing agent by controlling the molar ratio (1: 1) of the two and the reaction condition (NH) ₂ Has higher nucleophilicity compared with-OH), so that the-OH on the 4-amino-1-butanol does not participate in the reaction, and the specific reaction process is as follows:

s2, adding the intermediate and DMF into a three-neck flask, stirring at room temperature until the intermediate and DMF are completely dissolved, and adding K ₂ CO ₃ Powder of at least one member selected from the group consisting of N ₂ Heating and refluxing for 2h under the atmosphere, slowly dripping DMF solution of diethyl chlorophosphate into the solution, reacting for 6h at 56 ℃ after all dripping, pouring the reactant into deionized water to precipitate, washing for 3-4 times by using the deionized water, and placing the reactant in a vacuum oven for drying for 12h at 80 ℃ to obtain a reactive monomer; intermediate, DMF, K ₂ CO ₃ The ratio of the powder to the amount of the DMF solution of diethyl chlorophosphate is 14.5g:400mL:1.8g:34.4 mL; the mass concentration of the DMF solution of the diethyl chlorophosphate is 0.5 g/mL;

in the presence of a base (K) ₂ CO ₃ ) Under the action of (1), nucleophilic substitution reaction is carried out on-OH on the intermediate molecule and-Cl on the chloro diethyl phosphate molecule to generate a reaction type monomer, the obtained reaction type monomer contains-C = C, strong-polarity-CO-NH-group and phosphate ester group which can carry out subsequent polymerization reaction, and the reaction type monomer is phosphate ester derivative, and the reaction process is shown as follows;

s3, polymerizing the reactive monomer, AIBN and the metal complex in a system with an ethanol water solution (mass fraction of 60%) as a solvent at 60 ℃, after polymerizing for 2 hours, adding styrene into the reaction system under the protection of nitrogen, reacting for 5 hours, terminating the polymerization reaction by reducing the temperature, collecting the precipitate from the mixture, and drying the obtained precipitate in vacuum at 60 ℃ for 12 hours to obtain the auxiliary agent; the mass ratio of the reactive monomer, AIBN, metal complex and styrene is 30:1:0.1: 100;

under the action of metal complex (catalyst) and AIBN (initiator), the block-type polymer additive is obtained by a solution polymerization method, and the reaction process is as follows:

the obtained assistant is a block-type polymer assistant, the side chain of the molecule of the assistant contains strong polar-CO-NH-group and phosphate group, and also contains lipophilic benzene ring, therefore, the assistant can be regarded as a surfactant, and the heating and mixing temperature of the asphalt can be reduced by reducing the surface tension of the asphalt molecules; meanwhile, the compatibility of the polar additive and asphalt can be increased, so that the segregation phenomenon is not easy to occur, and the asphalt material has good storage stability under sealed storage;

in addition, the auxiliary agent is a macromolecular copolymerization block substance, has large molecular weight and long molecular chain, has a main chain consisting of single bonds and good flexibility, and can improve the flexibility of asphalt molecules due to the isolated double bonds (-C =0 and P = O) contained in the-CO-NH-group and the phosphate group, so that the flexibility of the asphalt molecules can be improved due to the addition of the auxiliary agent, the temperature node for converting the viscous elastic state of the asphalt into the glassy state can be reduced, and the asphalt has good relaxation property under the low-temperature condition;

in addition, the side chain of the obtained auxiliary agent molecule is introduced with phosphate ester group which is a phosphate ester derivative, and can promote the dehydration and carbonization of the high polymer material at high temperature or during combustion, so that the high polymer material can not generate combustible gas, and the carbonized material forms a protective carbon film to isolate the external air and heat, thereby improving the flame retardant property of the asphalt material.

The invention has the beneficial effects that:

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

Preparing an auxiliary agent:

s1, adding 7.2g of acrylic acid and 300mL of dichloromethane into a flask, adding 20g of EDCI (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, a condensing agent), stirring uniformly, adding 8.9g of 4-amino-1-butanol, stirring at normal temperature for reacting for 2h, performing rotary evaporation to remove a solvent, extracting with ethyl acetate, separating, and finally performing vacuum drying on a product at 60 ℃ for more than 3h to obtain an intermediate;

s2, 14.5g of intermediate and 400mL of DMF are added to a three-neck flask, stirred at room temperature until completely dissolved, and 1.8g of K is added ₂ CO ₃ Powder of at least one member selected from the group consisting of N ₂ Heating and refluxing for 2h under the atmosphere, slowly dripping 34.4mL of DMF solution of diethyl chlorophosphate into the solution, reacting for 6h at 56 ℃ after all dripping is finished, pouring reactants into deionized water to separate out a precipitate, washing for 3 times by using the deionized water, and placing the reactants in a vacuum oven to dry for 12h at 80 ℃ to obtain a reactive monomer; the mass concentration of the DMF solution of the diethyl chlorophosphate is 0.5 g/mL;

s3, polymerizing 30mmol of reactive monomer, 1mmol of AIBN and 0.1mmol of metal complex in 150mL of ethanol aqueous solution (mass fraction of 60%) at 60 ℃, after 2h of polymerization, adding 100mmol of styrene into the reaction system under the protection of nitrogen, reacting for 5h, terminating the polymerization reaction by reducing the temperature, collecting precipitate from the mixture, and drying the obtained precipitate at 60 ℃ in vacuum for 12h to obtain the assistant.

Example 2

Preparing an auxiliary agent:

s1, adding 14.4g of acrylic acid and 600mL of dichloromethane into a flask, adding 40g of EDCI (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, a condensing agent), stirring uniformly, adding 17.8g of 4-amino-1-butanol, stirring at normal temperature for reacting for 2h, performing rotary evaporation to remove a solvent, extracting with ethyl acetate, separating, and finally performing vacuum drying on a product at 60 ℃ for more than 3h to obtain an intermediate;

s2, 29g of intermediate and 800mL of DMF were added to a three-necked flask, and after stirring at room temperature until completely dissolved, 3.6g of K was added ₂ CO ₃ Powder of at least one member selected from the group consisting of N ₂ Heating and refluxing for 2h under the atmosphere, slowly dripping 68.8mL of DMF solution of diethyl chlorophosphate into the solution, reacting for 6h at 56 ℃ after all dripping is finished, pouring reactants into deionized water to separate out a precipitate, washing the reactants for 4 times by using the deionized water, and drying the reactants in a vacuum oven at 80 ℃ for 12h to obtain a reactive monomer; the mass concentration of the DMF solution of the diethyl chlorophosphate is 0.5 g/mL;

s3, polymerizing 60mmol of reactive monomer, 2mmol of AIBN and 0.2mmol of metal complex in 300mL of ethanol aqueous solution (mass fraction of 60%) at 60 ℃, after 2h of polymerization, adding 200mmol of styrene into the reaction system under the protection of nitrogen, reacting for 5h, stopping the polymerization reaction by reducing the temperature, collecting precipitate from the mixture, and drying the obtained precipitate at 60 ℃ in vacuum for 12h to obtain the assistant.

Example 3

The base layer of the tyre adopts long-fiber polyester non-woven fabrics impregnated by acrylic resin;

the isolating layer is a PE film;

the asphalt layer comprises the following raw materials: 55g of matrix asphalt, 20g of rubber oil, 15g of SBS elastomer, 2g of auxiliary agent prepared in example 1, 12g of talcum powder and 0.2g of anti-aging agent 4010;

the waterproof roll is prepared by the following steps:

putting matrix asphalt and rubber oil into a stirring tank, setting the stirring temperature to be 185 ℃, sequentially adding an SBS elastomer, an auxiliary agent and an anti-aging agent 4010, stirring at the speed of 200r/min for 3.5h to modify the asphalt, finally adding talcum powder, stirring for 1h, discharging at 185 ℃, coating an asphalt material on a base course layer which is soaked and extruded to form an asphalt layer while the asphalt material is hot, finally covering an isolation layer on the surface of the asphalt layer, and cooling, sizing and rolling to obtain the waterproof coiled material.

Example 4

the isolation layer is a PET film;

the asphalt layer comprises the following raw materials: 60g of matrix asphalt, 24g of rubber oil, 16.5g of SBS elastomer, 2.5g of auxiliary agent prepared in example 2, 13g of talcum powder and 0.25g of anti-aging agent 4010;

the waterproof roll is prepared by the following steps:

putting matrix asphalt and rubber oil into a stirring tank, setting the stirring temperature to be 185 ℃, sequentially adding an SBS elastomer, an auxiliary agent and an anti-aging agent 4010, stirring at the speed of 200r/min for 3.8 hours for asphalt modification, finally adding talcum powder, stirring for 1 hour, discharging at 185 ℃, coating an asphalt material on a base course layer which is soaked and extruded to form an asphalt layer while the asphalt material is hot, finally covering an isolation layer on the surface of the asphalt layer, and cooling, sizing and rolling to obtain the waterproof coiled material.

Example 5

the isolation layer is a PVC film;

the asphalt layer comprises the following raw materials: 65g of matrix asphalt, 28g of rubber oil, 18g of SBS elastomer, 3g of auxiliary agent prepared in example 1, 14g of talcum powder and 0.3g of anti-aging agent 4010;

the waterproof roll is prepared by the following steps:

putting matrix asphalt and rubber oil into a stirring tank, setting the stirring temperature to be 185 ℃, sequentially adding an SBS elastomer, an auxiliary agent and an anti-aging agent 4010, stirring at the speed of 200r/min for 4h to modify the asphalt, finally adding talcum powder, stirring for 1h, discharging at 185 ℃, coating asphalt materials on a base course layer which is soaked and extruded to form an asphalt layer while the asphalt materials are hot, finally coating an isolation layer on the surface of the asphalt layer, and cooling, sizing and rolling to obtain the waterproof coiled material.

Comparative example

The raw materials of the auxiliary agent in the example 3 are changed into SBS elastomer, and the rest raw materials and the preparation process are unchanged.

The following performance tests were carried out on the waterproofing membranes obtained in examples 3 to 5 and comparative example:

carrying out high temperature resistance test, low temperature flexibility limit test and seam peel strength test according to GB/T328-2007 test method for waterproof coiled materials for buildings;

the limit oxygen index of the asphalt materials prepared in the examples 3-5 and the comparative example is measured by adopting a YG-813 type oxygen index tester according to the oxygen index method of the plastic combustion performance test method (GB/T2406 + 1993);

the results obtained are shown in the following table:

	example 3	Example 4	Example 5	Comparative example
					High temperature resistance/105 ℃ for 2h	No flow and no drop	No flow and no drop	No flow and no drop	No flow and no drop
Low temperature flexibility	No crack at-57 DEG C	No crack at-60 DEG C	No crack at-58 DEG C	No crack at-43 DEG C
					Seam peel strength/N mm ^-1	2.15	2.36	2.25	2.01
Asphalt feed oxygen index/%)	28.5	28.9	28.7	18.5

The data in the table show that the composite waterproof coiled material prepared by the invention has excellent low-temperature flexibility, and the lowest low-temperature flexibility can reach-60 ℃; the high temperature resistance and the seam peel strength of the composite waterproof coiled material can meet higher requirements; the oxygen index of the obtained asphalt material is as high as 28.5 percent, which shows that the invention can effectively improve the flammability of asphalt and expand the application field of coiled materials; according to the data of the comparative example, the addition of the auxiliary agent can not only improve the low-temperature resistance of the composite waterproof roll material, but also improve the flammability characteristic of the asphalt material.

In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.

Claims

1. The utility model provides an ultra-low temperature self-adhesion rubber asphalt polymer composite waterproof coiled material, includes child basic unit, pitch layer and isolation layer, and the pitch layer soaks in the both sides surface of child basic unit, and the isolation layer covers on pitch layer surface, and its characterized in that, pitch layer include following part by weight raw materials: 55-65 parts of matrix asphalt, 20-28 parts of rubber oil, 15-18 parts of SBS elastomer, 2-3 parts of auxiliary agent, 12-14 parts of talcum powder and 0.2-0.3 part of anti-aging agent 4010;

wherein the auxiliary agent is prepared by the following steps:

s1, adding acrylic acid and dichloromethane into a flask, adding EDCI, stirring uniformly, adding 4-amino-1-butanol, stirring at normal temperature for reacting for 2 hours, performing rotary evaporation to remove a solvent, extracting with ethyl acetate, separating, and finally performing vacuum drying on the product at 60 ℃ for more than 3 hours to obtain an intermediate; the dosage ratio of the acrylic acid, the dichloromethane, the EDCI and the 4-amino-1-butanol is 7.2g to 300mL to 20g to 8.9 g;

s3, polymerizing the reactive monomer, AIBN and the metal complex in a system with an ethanol water solution as a solvent at 60 ℃, after polymerizing for 2 hours, adding styrene into the reaction system under the protection of nitrogen, reacting for 5 hours, terminating the polymerization reaction by reducing the temperature, collecting precipitates from the mixture, and drying the obtained precipitates in vacuum at 60 ℃ for 12 hours to obtain the auxiliary agent; the mass ratio of the reactive monomer, AIBN, metal complex and styrene was 30:1:0.1: 100.

2. The ultra-low temperature self-adhesive rubber asphalt polymer composite waterproof roll as claimed in claim 1, wherein the base layer is made of long fiber polyester non-woven fabric impregnated with acrylic resin.

3. The ultralow-temperature self-adhesive rubber asphalt polymer composite waterproof roll material as claimed in claim 1, wherein the isolating layer is one of a PE film, a PET film or a PVC film.

4. The ultra-low temperature self-adhesive rubber asphalt polymer composite waterproof roll material as claimed in claim 1, which is prepared by the following steps: