CN103030848A - Rubber/polyvinyl butyral mixed glue - Google Patents

Abstract

The invention discloses rubber/polyvinyl butyral mixed glue, and belongs to the technical field of rubber products. The mixed glue is prepared according to the following method: equally dividing 95 to 50 parts of rubber accounted in weight parts into two parts, and mixing the two parts of rubber at the temperature of 60 to 160 DEG C; after mixing, adding 5 to 50 parts of wasted polyvinyl butyral membranes and 0 to 20 parts of bulking agent into one part of rubber to continue mixing; and finally, adding the other part of rubber into the mixed rubber for alloying after mixing to obtain the rubber/polyvinyl butyral mixed glue. According to the invention, the mixed glue has a simple manufacturing process, and compared with the corresponding rubber products obtained through vulcanizing pure rubber, the vulcanized glue products obtained through vulcanizing the mixed glue are not lowered in comprehensive property, and in addition, the hardness and tearing strength of the rubber/polyvinyl butyral mixed glue products are improved remarkably. The mixed glue provided by the invention can effectively reduce the cost of rubber products, broaden the application scope of the wasted polyvinyl butyral membranes, and turn waste into wealth.

Description

A kind of rubber/polyvinyl butyral hybrid rubber

technical field

The invention relates to the technical field of rubber products, in particular to a rubber/polyvinyl butyral hybrid rubber with excellent performance, easy processing and low cost.

Background technique

Polyvinyl butyral is a resin formed by condensation of polyvinyl alcohol and n-butyraldehyde under the condition of strong acid as a catalyst. Because the condensation reaction is not complete, there is a certain amount of hydroxyl groups in the molecular chain of polyvinyl butyral; and because polyvinyl alcohol is obtained by hydrolysis of polyvinyl acetate, polyvinyl acetate cannot be hydrolyzed completely in the hydrolysis reaction, so There is a small amount of acetoxy groups; therefore, the macromolecular chain of polyvinyl butyral contains butyral groups, hydroxyl groups, and acetoxy terpolymers, but the content of acetoxy groups is usually very low (less than 2wt%). Polyvinyl butyral resin has many uses, and its most important application field is the production of safety glass interlayer diaphragm materials. More than 65% of the world's polyvinyl butyral resin production is used to produce automotive safety glass interlayer diaphragms. This polyvinyl butyral is a high-viscosity resin, and a large amount of softener (20-40 wt%) must be added during melt extrusion or casting into a film; in order to avoid degradation during processing and use , Add appropriate amount of heat stabilizer and light stabilizer in the production of polyvinyl butyral film. Therefore, polyvinyl butyral film has excellent impact resistance, cold resistance, weather resistance, good transparency and adhesion. Polyvinyl butyral films are widely used in automotive, construction and aviation, marine safety glass and solar photovoltaic module packaging film and other fields. With the rapid development of construction, automobile industry and photovoltaic industry, the amount of polyvinyl butyral film is increasing, which also produces a large amount of polyvinyl butyral scraps and polyvinyl butyral from the recycling of scrapped cars Scrap. With the increasing severity of raw material sources and environmental problems, the recycling of plastic waste has become the focus of global attention.

The polyvinyl butyral diaphragm contains more plasticizers, and at the same time, the polyvinyl butyral macromolecular chains or chains have strong hydrogen bonds. At room temperature, the polyvinyl butyral diaphragm has a similar elastic Viscoelastic properties, excellent impact resistance and cold resistance. Therefore, polyvinyl butyral films can replace elastomers to toughen plastics. Patent WO93102141 has reported the use of polyvinyl butyral film and compatibilizer to toughen polyolefins whose melting point is lower than the decomposition temperature of polyvinyl butyral; Ethylene propylene rubber and compatibilizer jointly toughen polypropylene; U.S. Patent 5770654 reports the use of polyvinyl butyral diaphragm and anhydride grafted EPDM rubber to toughen nylon; U.S. Patent 6506835B1 reports the use of polyvinyl alcohol Butyral membrane replaces part of the vinyl copolymer to toughen polyvinyl chloride; world patent WO2004/083307A1 reports the use of polyvinyl butyral membrane to toughen inorganic mineral-filled nylon; US patent 7138454 reports the use of polyvinyl alcohol Butyral diaphragm toughened glass fiber reinforced nylon. However, the toughening of plastics with polyvinyl butyral film has the following problems: (1) The thermal stability of polyvinyl butyral film is not high, and it begins to thermally decompose at 200 °C (A.K. Dhaliwal , J.N. Hay, The characterization of polyvinyl butyral by thermal analysis, Thermochimica Acta, 2002, 391: 245–255), and the processing temperature of plastics is usually higher, such as the processing temperature of polypropylene is about 230 ° C, used as engineering plastics The processing temperature of nylon is higher, that is, when polyvinyl butyral film is used to toughen most plastics, there is a problem that the processing temperature of the two does not match; (2) polyvinyl butyral film contains a large number of small molecular Plasticizer, in the process of blending with plastics and after the formation of blended materials, small molecule plasticizers are easy to migrate, especially for plastics that cannot contain plasticizers in products, polyvinyl butyral film does not Not applicable; (3) The polyvinyl butyral film increases the toughness of the plastic but reduces its rigidity, which is a common problem of elastomer toughened plastics (1.Cha Y J, Lee C H, Choe S, et al al. Morphology and mechanical properties of nylon 6 toughened with waste Poly(vinyl butyral) film[J]. Journal of Applied Polymer Science, 1998, 67, 1531-1540; 2. Ticiane S V, Nicole R D. residing Polymering toughenue of recycled windshield: PVB film as impact modifier[J]. European Polymer Journal, 2008, 44, 755–768.).

Compared with plastics, the processing temperature of rubber is lower, usually not exceeding 200 ° C, which is consistent with the processing temperature of polyvinyl butyral diaphragm; rubber is a typical polymer viscoelastic material, and polyvinyl butyral The mechanical properties of the diaphragm are similar; during the processing and use of rubber, a large amount of softener is usually added, and its effect is similar to that of the plasticizer in polyvinyl butyral diaphragm. At the same time, the price of most rubber is expensive, and people are trying their best to reduce the cost of their products without reducing the performance of rubber by adding other cheap polymers in rubber. Waste polyvinyl butyral film usually comes from the waste produced in the production of polyvinyl butyral film, the scraps produced in the production of safety glass, and the polyvinyl butyral film in the inner interlayer of scrapped automobile safety glass. These waste polyvinyl butyral diaphragms can no longer be used to produce interlayer films, but are often treated as waste, and the price is extremely low. Using rubber and waste polyvinyl butyral diaphragms together can obtain high-quality and low-cost rubber materials, but there is no relevant literature report at present.

Contents of the invention

In order to broaden the application fields of waste polyvinyl butyral diaphragms, the purpose of the present invention is to provide a high-quality and low-cost rubber blend prepared with rubber and recycled waste polyvinyl butyral diaphragms as main raw materials. vulcanized rubber.

Realize that the present invention adopts following method to prepare:

First divide 95-50 parts of rubber in parts by weight into two parts and knead at 60-160 ° C respectively, add 5-50 parts of waste polyvinyl butyral film, 0-20 parts of compatibilizer to one part Part blending, and finally add another part of the rubber after mixing and blending;

The rubber is one or more of nitrile rubber, styrene-butadiene rubber, natural rubber, butyl rubber, neoprene rubber, butadiene rubber, EPDM rubber or chlorinated polyethylene rubber.

The waste polyvinyl butyral film is the waste produced in the production of polyvinyl butyral film (such as the film with fish eyes), the leftover material produced in the production of safety glass, and comes from the safety glass of scrapped cars. Polyvinyl butyral membrane in interlayer.

The compatibilizer is maleic anhydride grafted EPDM rubber, maleic anhydride grafted styrene-butadiene thermoplastic elastomer, maleic anhydride grafted ethylene-vinyl acetate elastomer, maleic anhydride grafted ethylene-propylene elastomer one of the bodies. All are commercially available.

Compared with rubber, the polyvinyl butyral diaphragm has a lower viscosity during processing. In order to mix the two evenly, a segmented processing technology is adopted. First, part of the rubber is blended with the polyvinyl butyral diaphragm, and the resulting The product is further blended with the remaining rubber.

The invention has the following advantages: the used polyvinyl butyral diaphragm is waste polyvinyl butyral diaphragm, which is cheap and easy to obtain, and provides a new way for recycling the waste polyvinyl butyral diaphragm. The processing temperature of the rubber matches that of the polyvinyl butyral diaphragm, which also has the properties of an elastomer, which facilitates the mixing and processing of the rubber. The polyvinyl butyral is completely dispersed in the rubber matrix by the staged mixing process. It can be seen from Figure 1 that polyvinyl butyral is dispersed in the nitrile rubber matrix in the form of irregular particles. Because polyvinyl butyral is distributed in the rubber matrix as a dispersed phase, the entire blend system forms a spatial network structure after the rubber is crosslinked, and its mechanical properties are still not reduced. With the addition of an appropriate compatibilizer, the rubber blend The overall performance is excellent. The carbon-carbon chains in polyvinyl butyral are all saturated, so it has excellent weather resistance, and its oxidation resistance can be improved after blending with rubber containing double bonds in the molecular chain.

The processing technology of the present invention is simple, and the overall performance of the rubber product prepared by using the mixed rubber obtained in the embodiment of the present invention is not lower than that of the corresponding rubber product prepared from pure rubber, and the hardness and tear strength are obviously improved; the present invention can effectively reduce the Reduce the cost of rubber products, broaden the application range of waste polyvinyl butyral diaphragms, and turn waste into treasure. the

Description of drawings

Figure 1 is the SEM photo of the mixed rubber obtained in Example 11 (brittle fracture section in liquid nitrogen).

Detailed ways

The present invention will be described in detail below in conjunction with specific embodiments. In the examples, tensile properties are tested by GB/T 528-2009; tear properties are tested by GB/T529-2008; hardness is tested by GB/T23651-2009; oil resistance is tested by GB 1690.

Example 1

  Blending of nitrile rubber and polyvinyl butyral for the production of inner rubber for oil-resistant steel wire braided hoses

Divide 80 parts of nitrile rubber into two parts, and knead them in an internal mixer at 60°C for 5 minutes respectively, add 20 parts of polyvinyl butyral diaphragms to one part of the kneaded rubber and continue kneading for 10 minutes, then Then add another part of the mixed rubber and blend for 5 minutes to obtain the nitrile rubber/polyvinyl butyral mixed rubber.

 Performance test: Both the test sample and the control sample adopt the same compounding system and processing technology to prepare the test samples, and perform the performance test according to the unified national standard.

Test sample: steel wire braided hose inner rubber compound prepared by mixing the nitrile rubber/polyvinyl butyral compound obtained in this embodiment with rubber compounding agents.

Control sample: the steel wire braided rubber hose internal rubber mixed rubber prepared by mixing the same nitrile rubber used in the preparation of the mixed rubber in this embodiment and rubber compounding agent.

Table 1. Coordination table (parts by weight) of test sample and control sample in embodiment 1

raw material Test sample control sample The nitrile rubber/polyvinyl butyral hybrid glue prepared by the present embodiment 100 —— Nitrile rubber —— 100 stearic acid 3 3 Zinc oxide 5 5 Wear-resistant furnace black 75 75 sulfur 1.8 1.8 accelerator DM 1.5 1.5 Dibutyl phthalate 15 15 Antiager A 3 3 total 204.3 204.3

Table 2. The physical and mechanical properties of test sample and contrast sample in embodiment 1

physical and mechanical properties Test sample control sample Tensile strength / MPa 16.8 16.0 Elongation at break / % 382.1 380.0 Tensile set / % 5.8 6.0 Tear strength / kN/m 51.9 47.5 Hardness / Shore A 76 71 Resistance to oil mass change rate/ gasoline immersion +1.51 +1.62

Example 2 Blending of natural rubber, styrene-butadiene rubber and butadiene rubber with polyvinyl butyral for the production of tire tread rubber

Divide 35 parts of natural rubber, 10 parts of styrene-butadiene rubber and 20 parts of butadiene rubber into two parts, knead them in an internal mixer at 100°C for 10 minutes, and add 35 parts of polyvinyl alcohol to one part of the mixed rubber. After the butyral diaphragm and 20 parts of maleic anhydride grafted styrene-butadiene thermoplastic elastomer continue to knead for 9 minutes, another part of the kneaded rubber is added and blended for 10 minutes to obtain a rubber/polyvinyl butyral mixed rubber.

Performance test: Both the test sample and the control sample adopt the same matching system and processing technology to prepare test samples, and perform performance test according to the unified national standard.

Test sample: a rubber tire tread compound prepared by mixing the rubber/polyvinyl butyral compound obtained in this embodiment with the rubber compounding agent.

Control sample: the rubber tire tread rubber prepared by mixing the same rubber as the rubber used in the preparation of the mixed rubber in this embodiment with the rubber compounding agent. .

Table 3. Coordination table (parts by weight) of test sample and control sample in embodiment 2

raw material Test sample control sample Three kinds of rubber/polyvinyl butyral hybrid glues prepared by the present embodiment 100 —— natural rubber —— 55 SBR —— 30 Butadiene rubber —— 35 Zinc oxide 5 5 stearic acid 3 3 Antiaging agent 4010NA 1.5 1.5 Antiaging agent RD 1.5 1.5 High wear-resistant furnace black 55 55 engine oil 10 10 Accelerator NOBS 0.9 0.9 sulfur 1.5 1.5 total 178.4 178.4

Table 4. The physical and mechanical properties of test sample and contrast sample in embodiment 2

physical and mechanical properties Test sample control sample Tensile strength / MPa 24.5 22.3 Elongation at break / % 560.5 560.0 Tensile set / % 12.5 15.2 Tear strength / kN/m 108.4 95.6 Hardness / Shore A 70 60 Acron wear/cm ³ 0.135 0.157

Embodiment 3. Butyl rubber and EPDM rubber are blended with polyvinyl butyral diaphragm for the production of tire inner tube rubber

Divide 80 parts of butyl rubber and 15 parts of EPDM rubber into two parts, mix them in an internal mixer at 130°C for 15 minutes, add part of the mixed rubber to 5 parts of polyvinyl butyral diaphragm Continue blending with 5 parts of maleic anhydride grafted ethylene-propylene elastomer for 3 minutes, and then add another part of mixed rubber and blend for 10 minutes to obtain rubber/polyvinyl butyral hybrid rubber.

Performance test: Both the test sample and the control sample adopt the same matching system and processing technology to prepare test samples, and perform performance test according to the unified national standard.

Test sample: a rubber tire inner tube rubber prepared by mixing the rubber/polyvinyl butyral mixed rubber obtained in this embodiment with the rubber compounding agent.

Control sample: the rubber tire inner tube rubber prepared by mixing the same rubber as the rubber used in the preparation of the mixed rubber in this embodiment with the rubber compounding agent.

Table 5. Coordination table (parts by weight) of test sample and reference sample in embodiment 3

raw material Test sample control sample Two kinds of rubber/polyvinyl butyral hybrid glues prepared by the present embodiment 100 —— Butyl rubber —— 85 EPDM —— 15 Zinc oxide 5 5 stearic acid 1 1 Reinforced Furnace Black 65 65 Paraffin oil twenty two twenty two Accelerator TMTD 1.5 1.5 accelerator DM 0.5 0.5 sulfur 1.5 1.5 total 196..5 196..5

The physical and mechanical properties of test sample and control sample in table 6 embodiment 3

physical and mechanical properties Test sample control sample Tensile strength / MPa 11.6 9.2 Elongation at break / % 570.4 568.5 Tensile set / % 26.3 28.2 Tear strength / kN/m 43.8 40.6 Hardness / Shore A 57 54

Example 4 Blending of nitrile rubber and chloroprene rubber with polyvinyl butyral diaphragm for the production of glue for oil-resistant seals

Divide 40 parts of nitrile rubber and 50 parts of chloroprene rubber into two parts, and knead them in an internal mixer at 140°C for 2 minutes, and add 10 parts of polyvinyl butyral diaphragm and 10 parts of maleic anhydride grafted ethylene-vinyl acetate elastomer were blended for 20 minutes, and finally another part of the mixed rubber was added and blended for 5 minutes to obtain rubber/polyvinyl butyral mixed rubber.

Performance test: Both the test sample and the control sample adopt the same matching system and processing technology to prepare test samples, and perform performance test according to the unified national standard.

Test sample: the rubber for oil-resistant seal prepared by mixing the rubber/polyvinyl butyral mixed rubber obtained in this embodiment with the rubber compounding agent.

Control sample: the rubber used for oil-resistant seals prepared by mixing the same rubber as the rubber used in the preparation of the mixed rubber in this embodiment and the rubber compounding agent.

Table 7. Coordination table (parts by weight) of test sample and reference sample in embodiment 4

raw material Test sample control sample Two kinds of rubber/polyvinyl butyral hybrid glues prepared by the present embodiment 100 —— Nitrile rubber —— 50 Neoprene —— 50 Zinc oxide 5 5 magnesium oxide 3 3 stearic acid 1 1 Universal Furnace Black 65 65 Dibutyl sebacate 20 20 Antiager D 1.5 1.5 Cross-linking agent DCP 0.5 0.5 total 196 196

Table 8. The physical and mechanical properties of test sample and contrast sample in embodiment 4

physical and mechanical properties Test sample control sample Tensile strength / MPa 14.5 13.2 Elongation at break / % 361.8 342.7 Tensile set / % 6.8 7.0 Resistance to oil mass change rate/ gasoline immersion 10.6 13.2 Hardness / Shore A 65 60

Example 5 Use EPDM rubber and chlorinated polyethylene rubber to blend with polyvinyl butyral membrane for the production of glue for waterproof coils

Divide 40 parts of EPDM rubber and 10 parts of chlorinated polyethylene rubber into two parts, mix them in an internal mixer at 160°C for 5 minutes, add part of the mixed rubber to 50 parts of polyvinyl butyral film The sheet and 15 parts of maleic anhydride grafted EPDM rubber continued to be blended for 10 minutes, and then another part of the mixed rubber was added and blended for 8 minutes to obtain rubber/polyvinyl butyral mixed rubber.

Performance test: Both the test sample and the control sample adopt the same matching system and processing technology to prepare test samples, and conduct performance tests according to unified national standards.

Test sample: the rubber for waterproof membrane prepared by mixing the rubber/polyvinyl butyral mixed rubber obtained in this embodiment with the rubber compounding agent.

Control sample: use the same rubber as the rubber used in the preparation of the mixed rubber in this embodiment and the rubber compounding agent to prepare the waterproof membrane glue.

Table 9. Coordination table (parts by weight) of test sample and reference sample in embodiment 5

raw material Test sample control sample Two kinds of rubber/polyvinyl butyral hybrid glues prepared by the present embodiment 100 —— EPDM —— 60 Chlorinated polyethylene rubber —— 40 Zinc oxide 10 10 stearic acid 1 1 Universal Furnace Black 120 120 Ultrafine Talc Powder 30 30 Paraffin oil 90 90 Antiager MB 3 3 sulfur 1 1 accelerator DM 2.5 2.5 total 257.5 257.5

Table 10. The physical and mechanical properties of test sample and contrast sample in embodiment 5

physical and mechanical properties Test sample control sample Tensile strength / MPa 11.5 10.2 Elongation at break / % 503.0 501.3 Tear strength / kN/m 43 38 Hardness / Shore A 77 70

Example 11

Adopt 50 parts of nitrile rubber and 50 parts of polyvinyl butyral film mixing, other are the same as embodiment 1.

Claims (1)

1. Rubber and polyvinyl butyral mixed rubber, which is characterized in that it is prepared by the following method: first divide 95-50 parts of rubber by weight into two parts, and mix them at 60-160 °C respectively Refining, adding 5-50 parts of waste polyvinyl butyral diaphragm and 0-20 parts of compatibilizer to a part of it for blending, and finally adding another part of rubber after kneading and blending; The rubber is one or more of nitrile rubber, styrene-butadiene rubber, natural rubber, butyl rubber, neoprene, butadiene rubber, EPDM rubber or chlorinated polyethylene rubber; The waste polyvinyl butyral film is the waste produced in the production of polyvinyl butyral film, the leftover material produced in the production of safety glass or the polyvinyl butyral film in the inner interlayer of scrapped automobile safety glass piece; The compatibilizer is EPDM rubber grafted with maleic anhydride, styrene-butadiene thermoplastic elastomer grafted with maleic anhydride, ethylene-vinyl acetate elastomer grafted with maleic anhydride or ethylene-propylene rubber grafted with maleic anhydride body.