阅读说明：本技术 一种抗开裂的非沥青型防水卷材及其制备工艺 (Cracking-resistant non-asphalt waterproof coiled material and preparation process thereof ) 是由 孙冰 贾康 李霞 于 2021-10-12 设计创作，主要内容包括：本发明公开了一种抗开裂的非沥青型防水卷材及其制备工艺,防水卷材包括以下质量份数的原料：HDPE100份；增塑剂7～10份；碳酸钙32～36份；EVA热熔胶49～52份；矿物粒8～11份；改性纤维2～4.6份；所述改性纤维以涤纶透气纤维经过处理液低温冻结处理得到,所述处理液中NaOH浓度为0.3～0.52mol/L；所述改性纤维长度与卷材的厚度比为0.6～1,制备方法为将原料加入混合机中高速混合后经过熔融、流延、辊压、定型后得到产品防水卷材,本申请抗开裂的防水卷材加入本申请的改性纤维后,使得防水卷材减少产生裂纹以及阻碍冻融循环下裂纹的继续深入,继而保护防水卷材的防水性能。(The invention discloses a cracking-resistant non-asphalt waterproof coiled material and a preparation process thereof, wherein the waterproof coiled material comprises the following raw materials in parts by weight: 100 parts of HDPE; 7-10 parts of a plasticizer; 32-36 parts of calcium carbonate; 49-52 parts of EVA hot melt adhesive; 8-11 parts of mineral particles; 2-4.6 parts of modified fiber; the modified fiber is obtained by freezing treatment liquid at low temperature through polyester breathable fiber, wherein the concentration of NaOH in the treatment liquid is 0.3-0.52 mol/L; the modified fiber length is 0.6-1 with the thickness ratio of coiled material, and the preparation method is to add the raw materials into the mixing machine and obtain the product waterproof coiled material after melting, curtain coating, roll-in, design after mixing at a high speed, and the waterproof coiled material of this application anti-cracking adds the modified fiber of this application after for waterproof coiled material reduces and produces the crackle and hinders the continuation of crackle deep under the freeze-thaw cycle, then protects waterproof coiled material's waterproof performance.)

1. The anti-cracking waterproof roll is characterized by comprising the following raw materials in parts by weight, and is obtained by mixing and heating tape casting:

100 parts of HDPE;

7-10 parts of a plasticizer;

32-36 parts of calcium carbonate;

49-52 parts of EVA hot melt adhesive;

8-11 parts of mineral particles;

2-4.6 parts of modified fiber;

the modified fiber is obtained by freezing treatment liquid at low temperature by using the terylene breathable fiber,

the concentration of NaOH in the treatment solution is 0.3-0.52 mol/L;

the ratio of the length of the modified fiber to the thickness of the coiled material is 0.6-1.

2. The anti-cracking waterproof roll material as claimed in claim 1, wherein KCl is further added into the treatment fluid, and the concentration of KCl is 0.21-0.38 mol/L.

3. The crack-resistant waterproof roll as claimed in claim 2, wherein the concentration of NaOH in the treatment solution is 0.43mol/L, and the concentration of KCl in the treatment solution is 0.31 mol/L.

4. The anti-cracking waterproof roll material as claimed in claim 1, wherein the length of the modified fibers is 3-5 mm.

5. The anti-cracking waterproof roll material as claimed in claim 1, wherein the raw material of the modified fiber, namely the breathable polyester fiber, is subjected to antistatic treatment by using an antistatic agent before treatment by the treatment liquid, and the antistatic agent is a non-silane coupling type antistatic agent.

6. The anti-cracking waterproof roll material as claimed in claim 1, wherein the antistatic agent is octadecylamine polyoxyethylene ether.

7. A preparation process of the anti-cracking waterproof roll material as claimed in any one of claims 1 to 6, which is characterized by comprising the following steps:

s1, adding the raw materials into a mixer, and mixing at a high speed at 40-50 ℃ for 5-30 min;

s2, melting, casting, rolling and shaping the mixed raw materials to obtain the waterproof roll, wherein the melting temperature is 180-200 ℃.

Technical Field

The invention relates to the field of organic waterproof materials, in particular to a cracking-resistant non-asphalt waterproof coiled material and a preparation process thereof.

Background

The waterproof roll is mainly used for building walls, roofs, tunnels and the like, can be curled into a roll-shaped flexible building material product for resisting external rainwater and underground water leakage, is used as a leakage-free connection between an engineering foundation and a building, is a first barrier for waterproofing of the whole engineering, and plays a vital role in the whole engineering.

The waterproof coiled material is another high-molecular organic material which is different from the traditional asphalt waterproof coiled material based on the aesthetic or design requirements, and is prepared by taking HDPE as a main organic base material and matching with inorganic filler, a binder and other auxiliary agents such as a thickening agent.

The inventor of the application finds that the waterproof coiled material has good fracture resistance at room temperature or outdoor temperature of more than 20 ℃, but the fracture resistance is embodied in overall fracture resistance, and the fracture resistance is poor after fine cracks are generated. This kind of waterproofing membrane is ageing very fast because the one side that is located external environment, easily produces the crackle, and its crackle can not once only crack waterproofing membrane from the coiled material thickness, but can make liquid flow in the crackle, and ambient temperature is undulant about the freezing point of liquid freezes, can form freeze thawing cycle, further deepens the crackle, makes waterproofing membrane waterproof nature greatly decline or waterproof nature destroyed, current organic material waterproofing membrane finally.

Disclosure of Invention

The invention aims to solve the problem that the existing non-asphalt waterproof coiled material is easy to damage the waterproof property due to deep cracks after the cracks are generated, and provides an anti-cracking non-asphalt waterproof coiled material and a preparation process thereof.

In a first aspect, the invention provides a cracking-resistant non-asphalt waterproof coiled material, which is realized by adopting the following scheme: the cracking-resistant non-asphalt waterproof coiled material is prepared by mixing, heating and tape casting the following raw materials in parts by weight:

100 parts of HDPE;

7-10 parts of a plasticizer;

32-36 parts of calcium carbonate;

49-52 parts of EVA hot melt adhesive;

8-11 parts of mineral particles;

2-4.6 parts of modified fiber;

the modified fiber is obtained by freezing treatment liquid at low temperature by using the terylene breathable fiber,

the concentration of NaOH in the treatment solution is 0.3-0.52 mol/L;

the ratio of the length of the modified fiber to the thickness of the coiled material is 0.6-1.

By adopting the technical scheme, the pore cavities are formed in the polyester breathable fibers, and air is filled in the pore cavities, in the application, the polyester breathable fibers are subjected to low-temperature freezing treatment by the treatment liquid, sodium hydroxide crystals precipitated during freezing can penetrate into the polyester breathable fibers along with freeze-thaw cycles, and modified fibers with a large number of fine pores communicated with the pore cavities on the surfaces are obtained,

HDPE melts in this application waterproofing membrane production process, and modified fiber will be discharged by the gas in the vestibule of intercommunication under the heating pressurization (receive outside melting HDPE extrusion pressurized), so make the fibre surface sunken. The maximum sunken depth can reach 0.3 times of fiber diameter, and the sunken depth is intensively distributed in 0.21-0.26 times of fiber diameter, so that the outer side surface of the modified fiber and the organic base material of the waterproof roll can be connected and fixed at high strength in a micron order, and a foundation is provided for providing tension for the modified fiber and preventing the waterproof roll from generating cracks.

Meanwhile, NaOH crystal puncture sites are uniform on the basis of the whole fiber, and for micron-sized fiber sections, the NaOH crystal puncture sites are not uniform, so that the distribution of depressions on the surface of the fiber is not uniform, the lengths of the depressions along the length of the fiber are different, but the NaOH crystal puncture sites are small, the damage to the tensile strength of the surface of the fiber is small, the depressions are formed by spontaneous depressions of the fiber instead of external cutting damage, and the strength of the fiber sections at the depressions is increased rather than reduced compared with that of the fiber sections at other positions without depressions, and then the fiber sections are combined with the waterproof coiled material through the surface of the fiber.

This is not possible with external plasma treatment, which is not "stable" to obtain fibers with a cavity depth of 0.21 to 0.26 times the diameter. On one hand, when the fiber is obtained by plasma treatment and other methods, a large amount of fibers with the defect depth larger than 0.5 time of the diameter and broken fibers are generated, even the fibers are fused together, and a large amount of static electricity is carried and is not easy to disperse; on the other hand, the strength of the fiber is reduced, and the effect is not good.

The modified fibers are short in length and are not mixed in the coiled material orderly, the mixing modes are various, and the modified fibers are bent, straight and coiled and are not spread along the surface of the coiled material, so that tensioning prestress is uniformly distributed in all dimension directions of the coiled material;

meanwhile, the glass fiber mesh cloth is different from the glass fiber mesh cloth in the existing asphalt waterproof coiled material and enhances the integral breaking strength of the waterproof coiled material, the asphalt material has the capability of self-repairing by heating as a fluid, the glass fiber mesh cloth distributed on the integral plane can effectively guide the self-repairing of the asphalt material in the waterproof coiled material of the asphalt material, but when the glass fiber mesh cloth is used for the waterproof coiled material with HDPE as an organic base material, the expansion and contraction coefficients of the waterproof coiled material are different due to the temperature difference, and the cracks are more serious; the modified fiber is short, the tension force at a multi-dimensional angle is provided, and the generation and the penetration of cracks are effectively reduced.

To sum up, this application anti cracked waterproofing membrane adds behind the modified fiber of this application for waterproofing membrane reduces to produce the crackle and hinders continuation deep of crackle under the freeze thawing cycle, then protects waterproofing membrane's waterproof performance.

Optionally, KCl is also contained in the treatment liquid, and the concentration of the KCl is 0.21-0.38 mol/L.

Optionally, the concentration of NaOH in the treatment solution is 0.43mol/L, and the concentration of KCl in the treatment solution is 0.31 mol/L.

By adopting the technical scheme, KCl is added into the treatment liquid, and the treated modified fiber has better improvement effect on the waterproof coiled material taking HDPE as the organic base material, wherein the effect is better when the concentration of NaOH is 0.43mol/L and the concentration of KCl is 0.31 mol/L.

Optionally, the length of the modified fiber is 3-5 mm.

By adopting the technical scheme, the rear degree of the existing coiled material is within the range of 1.35-5 mm, the waterproof coiled material is generally 2-5 mm, the length of the modified fiber is 3-5 mm, the coiled material is not easy to be coiled in a mixing process or a casting process, and is wound mutually, normal in head and tail, good in distribution and better in anti-crack effect.

Optionally, the raw material polyester breathable fiber of the modified fiber is subjected to antistatic treatment by using an antistatic agent before treatment of the treatment liquid, and the antistatic agent is a non-silane coupling type antistatic agent.

By adopting the technical scheme, the modified fiber subjected to antistatic treatment is easier to disperse and convenient to mix in the process of mixing with other raw materials, and simultaneously seems to be beneficial to the organic combination of the modified fiber and HDPE and the like. In addition, silane coupling type antistatic agent is not applicable to the application, and experiments show that silane coupling type antistatic agent has a blocking effect on the freezing and thawing puncture hole cavity of the treatment fluid, so that silane coupling type antistatic agent cannot be used.

Optionally, the antistatic agent is octadecylamine polyoxyethylene ether.

By adopting the technical scheme, the octadecylamine polyoxyethylene ether has a good effect when being used as an antistatic agent.

In a second aspect, the invention provides a preparation process of a cracking-resistant waterproof roll, which is realized by adopting the following scheme: the preparation process of the anti-cracking waterproof roll comprises the following steps:

s1, adding the raw materials into a mixer, and mixing at a high speed at 40-50 ℃ for 5-30 min;

and S2, melting, casting, rolling and shaping the mixed raw materials to obtain the waterproof roll.

By adopting the technical scheme, the waterproof coiled material has good performances of crack resistance and crack deepening resistance.

In conclusion, the invention has the following beneficial effects:

1. after the modified fiber is added into the anti-cracking waterproof coiled material, cracks are reduced and the continuous penetration of the cracks under freeze-thaw cycle is prevented, so that the waterproof performance of the waterproof coiled material is protected;

2. the modified fiber with the length of 3-5 mm is not easy to roll in the mixing process or the casting process, namely the modified fiber is wound with each other, the end of the modified fiber is always human, the modified fiber is well distributed, and the anti-crack effect is better;

3. modified fiber through antistatic treatment is changeed the dispersion at the in-process of mixing with other raw materials, and convenient the mixing helps organic combination such as modified fiber and HDPE, further improves the waterproof performance protection effect of this application waterproofing membrane.

Detailed Description

Preparation example 1

A modified fiber is prepared by the following steps:

soaking polyester breathable fibers with the length of 4mm and the diameter of 50 +/-2 mu m into treatment liquid, and applying force to keep the polyester breathable fibers soaked in the treatment liquid, wherein the treatment liquid is a mixed solution of NaOH and KCl, the concentration of NaOH is 0.43mol/L, and the concentration of KCl is 0.31 mol/L;

and (3) cooling and freezing the treatment liquid mixed with the polyester breathable fibers, freezing for 2h, then heating and unfreezing in a natural environment, so that one-time freezing and unfreezing is adopted as a freezing and thawing process, repeated operation is carried out for 5 times in total, and the fibers are fished out and naturally dried to obtain the modified fibers.

Preparation examples 2 to 7

A modified fiber, which is different from the modified fiber of example 1 in the length of the polyester air-permeable fiber as the raw material and the concentration of the component in the treatment liquid. The process parameters of the modified fibers of preparation examples 1-7 are shown in the following table.

TABLE I modified fiber Process parameter tables in preparation examples 1 to 7

	Preparation example 1	Preparation example 2	Preparation example 3	Preparation example 4	Preparation example 5	Preparation example 6	Preparation example 7
								Length of fiber/μm	4	4	4	3	5	6	2
NaOH concentration/mol. L-1	0.43	0.3	0.52	0.43	0.43	0.43	0.43
								KCl concentration/mol. L-1	0.31	0.21	0.38	0.31	0.31	0.31	0.31

Further, production examples 8 to 12 were also included.

Preparation examples 8 to 12

A modified fiber is prepared by the following steps:

soaking the terylene breathable fiber with the diameter of 50 +/-2 mu m in the static removing liquid for 20min, fishing out after the soaking is finished, and naturally drying to obtain the static removing fiber. The destaticizing liquid is an aqueous solution of an antistatic agent.

Soaking the prepared static electricity removing fiber into a treatment solution, and applying force to keep the terylene breathable fiber soaked in the treatment solution, wherein the treatment solution is a mixed solution of NaOH and KCl.

And (3) cooling and freezing the treatment liquid mixed with the polyester breathable fibers, freezing for 2h, then heating and unfreezing in a natural environment, so that one-time freezing and unfreezing is adopted as a freezing and thawing process, repeated operation is carried out for 5 times in total, and the fibers are fished out and naturally dried to obtain the modified fibers. The modified fibers of preparation examples 8-12 have the following process parameters.

TABLE II modified fiber Process parameter tables of preparation examples 8 to 12

Examples 1 to 11

The anti-cracking waterproof roll comprises the following raw materials in parts by mass: 100 parts of HDPE, 8 parts of plasticizer, 35 parts of calcium carbonate, 50 parts of EVA hot melt adhesive, 9 parts of mineral particles and 3.8 parts of modified fiber.

The preparation process comprises the following steps:

s1, adding the raw materials into a mixer, and mixing at a high speed at 40-50 ℃ for 5-30 min;

s2, melting, casting, rolling and shaping the mixed raw materials to obtain the waterproof roll product, wherein the melting temperature is 188 ℃.

The plasticizer is phthalate, the mineral particles are kaolin powder, and the particle sizes of the kaolin powder and the calcium carbonate are both 80 +/-5 mu m.

Examples 1-12 differ in the source of the modified fiber. The modified fiber sources in examples 1-12 are shown in Table three below.

TABLE III production Process parameters for examples 1 to 12

Example 1

Example 2

Example 3

Example 4

Example 5

Example 6

Modified fiber sources

Preparation example 1

Preparation example 2

Preparation example 3

Preparation example 4

Preparation example 5

Preparation example 6

Example 7

Example 8

Example 9

Example 10

Example 11

Modified fiber sources

Preparation example 7

Preparation example 8

Preparation example 9

Preparation example 11

Preparation example 12

Examples 12 to 15

The anti-cracking waterproof roll material is characterized by other raw material dosage and modified fiber source based on the embodiment 1. The following Table four shows the raw material parameters of examples 12 to 15.

TABLE IV raw material parameters of examples 12 to 15

	Example 12	Example 13	Example 14	Example 15
					Modified fiber sources	Preparation example 1	Preparation example 1	Preparation example 9	Preparation example 9
HDPE/kg	100	100	100	100
					Plasticizer/kg	7	10	7	9
Calcium carbonate/kg	32	36	32	35
					EVA Hot melt adhesive/kg	49	52	49	50
Mineral particles/kg	8	11	8	10
					Modified fiber/kg	2	4.6	2	4.5

Example 16

A crack-resistant waterproof coiled material is characterized in that based on the embodiment 1, the processing liquid is NaOH solution, and the concentration of NaOH is 0.43 mol/L.

Example 17

A crack-resistant waterproof coiled material is characterized in that based on the embodiment 1, the processing liquid is NaOH solution, and the concentration of NaOH is 0.21 mol/L.

Example 18

A crack-resistant waterproof coiled material is characterized in that based on the embodiment 1, the processing liquid is NaOH solution, and the concentration of NaOH is 0.38 mol/L.

Comparative example 1

The anti-cracking waterproof roll is based on example 1, and is characterized in that the polyester breathable fibers are directly used instead of modified fibers.

Comparative example 2

The anti-cracking waterproof roll is based on example 4, and is characterized in that the polyester breathable fibers are directly used instead of modified fibers.

Comparative example 3

Based on example 5, the waterproof roll with crack resistance is characterized in that the polyester breathable fibers are used to directly replace modified fibers.

Comparative example 4

A crack-resistant waterproof roll material, based on example 1, except that the modified fiber is obtained from preparation example 10.

Comparative example 5

Based on example 12, the waterproof roll with crack resistance is characterized in that the polyester breathable fibers are used to directly replace modified fibers.

Comparative example 6

Based on example 13, the waterproof roll with crack resistance is characterized in that the polyester breathable fibers are used to directly replace modified fibers.

The test data of the examples 1 to 15 and the comparative examples 1 to 6 are shown in the fifth and sixth tables after the freeze-thaw crack resistance deepening test.

[ test for deepening of crack by freezing and thawing ]

1. And (3) spreading a test coiled material of 0.8m by 0.8m, and cutting cracks on the coiled material by using a sample cutter, wherein the opening depth is 1mm, the length of each crack is 2mm, the cracks are uniformly distributed at intervals, and the distribution interval is 8 cm.

2. And (3) taking the simulated crack sample which is not subjected to the waterproof and compression-resistant test after the No. 1 step, performing freeze-thaw treatment, wherein the freeze-thaw treatment is to horizontally unfold the treated sample and immerse the sample in water, the water surface is 2cm higher than the upper surface of the sample, cooling to completely freeze the water, freezing for 30min and then naturally melting, repeatedly freezing and thawing after the water temperature reaches 15 ℃, circulating for 50 times to obtain the freeze-thaw crack sample, and performing the waterproof and compression-resistant test.

The sample cutter includes the clamp plate and the fixed blade that is located clamp plate side, and the part that the blade is located the clamp plate outside is the thorn piece, and the thorn piece is the rectangle, and the long limit of rectangle is on a parallel with the clamp plate and long limit length is 2mm, and the perpendicular clamp plate of minor face and minor face length of rectangle are 1 mm. The number of the blades is multiple, the blades and the barbed sheets are distributed on the pressing plate in a rectangular array, the barbed sheets in each row are parallel to each other, and the spaces between every two rows are 2 cm; the barbed sheets of each row are positioned on the same plane, and the spaces between every two rows are 2 cm.

The waterproof and compression-resistant test method refers to GB/T328.10-2007 test method 10 part of building waterproof coiled materials: a method B in the water impermeability of asphalt and polymer waterproof coiled materials selects a 7-hole round disc for experiment, and the experimental result is measured by water pressure and water permeation time. (pass failure to permeate water within a specified time in Standard)

TABLE VI Damage crack deepening test results of examples 1 to 15 and comparative examples 1 to 7

	Example 1	Example 2	Example 3	Example 4	Example 5	Example 6
							(0.34MPa water pressure) water permeation time/min	62	49	67	47	53	41
(0.42MPa water pressure) water permeation time/min	46	37	50	35	40	31
								Example 7	Practice ofExample 8	Example 9	Example 10	Example 11	Example 12
(0.34MPa water pressure) water permeation time/min	31	80	99	63	72	53
							(0.42MPa water pressure) water permeation time/min	23	60	74	47	54	39
	Example 13	Example 14	Example 15	Example 16	Example 17	Example 18
							(0.34MPa water pressure) water permeation time/min	70	77	88	53	58	59
(0.42MPa water pressure) water permeation time/min	53	56	65	40	42	43
								Comparative example 1	Comparative example 2	Comparative example 3	Comparative example 4	Comparative example 5	Comparative example 6
(0.34MPa water pressure) water permeation time/min	24	25	24	27	21	23
							(0.42MPa water pressure) water permeation time/min	17	19	18	20	16	17

By combining example 1, comparative example 1 and table six, it can be seen that the water penetration time of example 1 is far longer than that of comparative example 1 after the modified fiber is added; by combining example 4, comparative example 2 and table six, it can be seen that the water penetration time of example 2 is far longer than that of comparative example 2 after the modified fiber is added; by combining example 5, comparative example 3 and table six, it can be seen that the water penetration time of example 5 is far longer than that of comparative example 3 after the modified fiber is added in the application; the modified fiber is added, so that compared with unmodified fiber, freeze-thaw cycle after the modified fiber is added obviously reduces damage to the waterproof property of the waterproof roll with cracks, and the waterproof property of the waterproof roll is protected.

By combining the example 1, the example 2 and the example 3, it can be known that when the thickness of the coil is 5mm, the concentration of NaOH and KCl in the treatment solution is 0.43mol/L and 0.31mol/L, and the obtained modified fiber is added into the raw materials of the present application, and then has a good waterproof protection effect on the waterproof coil under the synergistic effect of the modified fiber and other raw materials.

It can be seen from the combination of examples 1, 4, 6 and 7 that the modified fibers in examples 6, 4, 1, 5 and 7 have sequentially increased lengths, but the waterproof protection effect is firstly increased and then weakened after being increased by more than 4mm, and the waterproof protection effect is obviously reduced after being increased by 6 mm. Therefore, the length of the modified fiber is 3-5 mm, the modified fiber can have good improvement effect, 3-5 mm of the modified fiber is preferably used, and the ratio of the length of the modified fiber to the thickness of the coiled material is 0.6-1.

By combining the examples 1, 8 and 9, the waterproof performance of the waterproof rolls of the examples 8 and 9 is better than that of the waterproof rolls of the example 1 under the freeze-thaw crack deepening test; by combining the examples 4, 5, 10 and 11, it can be seen that the waterproof performance of the waterproof roll of example 10 is better than that of example 4 in the freeze-thaw crack deepening test, and the waterproof performance of the waterproof roll of example 11 is better than that of example 5 in the freeze-thaw crack deepening test; the antistatic agent is selected for treatment, so that the modified fiber subjected to antistatic treatment is easier to disperse and convenient to mix in the process of mixing with other raw materials, and meanwhile, the antistatic treatment seems to be beneficial to the organic combination of the modified fiber and HDPE and the like.

Comparative example 4 waterproof performance of the waterproof roll under the freeze-thaw crack deepening experiment is inferior to that of example 1, and the applicant finds that silane coupling agent substances are not suitable for the application and have a blocking effect on the freeze-thaw puncture cavity of the treatment solution through trying other silane coupling type antistatic agents, so that the silane coupling agent substances cannot be used.

In addition, the octadecylamine polyoxyethylene ether used in example 9 among the available antistatic agents has a good effect.

It can be known from the combination of embodiment 1 and embodiments 16 to 18 that, when the modified fiber is obtained, the KCl is added into the treatment solution, so that the waterproof protection effect of the modified fiber on the waterproof roll material can be further improved, and the concentration of KCl is preferably 0.31 mol/L.

By combining the examples 10-15 and the comparative examples 5-6, the improved method disclosed by the application comprises the following raw materials in parts by mass: 100 parts of HDPE; 7-10 parts of a plasticizer; 32-36 parts of calcium carbonate; 49-52 parts of EVA hot melt adhesive; 8-11 parts of mineral particles; the modified fibers have better waterproof protection effect within the range of 2-4.6 parts.

The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.