CN109810451B - Water-soluble rubber and preparation method thereof - Google Patents
Water-soluble rubber and preparation method thereof Download PDFInfo
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- CN109810451B CN109810451B CN201811638950.1A CN201811638950A CN109810451B CN 109810451 B CN109810451 B CN 109810451B CN 201811638950 A CN201811638950 A CN 201811638950A CN 109810451 B CN109810451 B CN 109810451B
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Abstract
The invention provides water-soluble rubber and a preparation method thereof, wherein the water-soluble rubber is mainly prepared from the following components in parts by weight: the paint is mainly prepared from the following components in parts by weight: 35-55 parts of acrylamide modified polyurethane, 20-30 parts of carboxymethyl chitosan, 5-40 parts of a compatilizer, 0.3-2 parts of a coupling agent, 0.1-1 part of an antioxidant, 1-5 parts of a softener, 0.3-3 parts of a crosslinking agent, 0.3-3 parts of an accelerator and 0.5-6 parts of sulfur. The water-soluble rubber provided by the invention has certain rubber elasticity and strength and good solubility, can be dissolved in water by controlling the dissolution time and the strength retention rate through controlling the proportion of materials, provides customized products for customers in the military industry field and the petroleum field, and has higher economic value and social value.
Description
Technical Field
The invention relates to the field of functional polymer materials, in particular to water-soluble rubber and a preparation method thereof.
Background
At present, along with the rapid development of the technology, the water-swelling rubber gradually develops and matures, is widely applied to waterproof and leak-stopping rubber sealing products, and solves the problem of untight sealing. However, under specific scenes in the fields of petrochemical industry, military industry, highways and the like, the rubber material after the rubber material plays a role in providing soluble or disappearing performance requirements, namely the demand for water-soluble rubber materials is increasingly strong.
Water-soluble rubber materials are mainly used for tool seals and soluble tools. At present, water-soluble polymer rubber materials rarely appear in the market, and although foreign companies occasionally make products, the products have high limitations, and more importantly, the problems of strength, solubility and environmental pollution of the products are difficult to be considered. With the development of the oil and gas well reservoir transformation technology, the downhole tool applied to the oil and gas well reservoir transformation technology develops from drillable to soluble direction, and the soluble materials of the current downhole tool for oil and gas well reservoir transformation comprise the following materials: soluble rubber materials, soluble plastic materials, soluble metal-nonmetal composite materials, and particularly water-soluble rubber products have strong market demands. At present, however, the water-soluble rubber materials on the market are few, the performance is not good, and the development of the water-soluble rubber which can be controlled within a certain temperature and time is more rarely reported.
Therefore, the existing water-soluble rubber needs to be improved.
Disclosure of Invention
The invention provides novel water-soluble rubber and a preparation method thereof, the water-soluble rubber has good solubility and mechanical strength, and the problem that the existing rubber cannot be dissolved or has poor solubility is solved.
The technical scheme of the invention is realized as follows:
the invention provides water-soluble rubber which is mainly prepared from the following components in parts by weight:
35-55 parts of acrylamide modified polyurethane (AM-PU), 20-30 parts of carboxymethyl chitosan, 5-40 parts of compatilizer, 0.3-2 parts of coupling agent, 0.1-1 part of antioxidant, 1-5 parts of softener, 0.3-3 parts of crosslinking agent, 0.3-3 parts of accelerator and 0.5-6 parts of sulfur.
In the formula, the easily hydrolyzed material polyurethane is used as a matrix, and the grafted acrylamide macromolecule hydrophilic chain segment is adopted, so that the main chain polyurethane has certain rubber elasticity and strength, and the grafted acrylamide has the characteristic of being dissolved in water. Meanwhile, the natural water-soluble material carboxymethyl chitosan is added to initiate the water-soluble disintegration of the material, namely the material is very easy to absorb water at the initial stage of dissolution, and the water absorption speed and the dissolution time can be controlled by controlling the proportion of different materials, so that the speed of the reduction of the rubber strength is controlled, the controllability of the hydrolysis performance of the rubber is realized, and a customized product is provided for customers in the military industry field and the petroleum field. And under the coordination action with other components in the formula, the carboxymethyl chitosan can increase the water absorption speed of the material, and the acrylamide modified polyurethane can delay the dissolution speed and the strength retention rate of the material.
Preferably, the compatilizer is composed of polyvinyl alcohol grafted glycidyl methacrylate (PVA-g-GMA), or maleic anhydride grafted SBS, maleic anhydride grafted SEBS and other systems, and is favorable for compatibility and dispersion between hydrophilic chain segment and hydrophilic chain segment components in the components.
Preferably, in the compatilizer, the mass ratio of the polyvinyl alcohol grafted glycidyl methacrylate to the maleic anhydride grafted SBS (or maleic anhydride grafted SEBS) is 3: 1-5: 1. the compatilizer in the proportion ensures the compatibility and dispersion between the hydrophilic chain segment and the lipophilic chain segment in the main component, and simultaneously, the water solubility of the compatilizer on the whole is not influenced by the higher proportion of the polyvinyl alcohol grafted glycidyl methacrylate.
Preferably, the number average molecular weight of the acrylamide modified polyurethane resin is 0.5 to 6.5 ten thousand. The performance of the acrylamide modified polyurethane resin material with the molecular weight distribution is similar to that of common natural rubber and styrene butadiene rubber materials, and the performance requirements of rubber materials in most application scenes can be met.
Preferably, the carboxymethyl chitosan product is granular or powder, the mesh number is 300-1500 meshes, and the dispersion performance and the water absorption performance of the carboxymethyl chitosan with the parameters are excellent. Too low particle size is not beneficial to the dispersion of the particles in the elastic material, and too large particle size has poor water absorption effect and cannot achieve controllable dissolution effect.
Preferably, the coupling agent is a titanate coupling agent or an aluminate coupling agent.
Preferably, the antioxidant consists of 1010, 168 and HP-136 in a weight ratio of 1:1.5: 1. The invention utilizes the synergistic effect of the three antioxidants, fully exerts the advantages of the antioxidants, provides excellent oxidation resistance for water-soluble rubber, ensures the performance stability of the water-soluble rubber, prolongs the quality guarantee period of the material, and avoids the influence of oxidative degradation on the service performance of the water-soluble rubber in the processes of storage, transportation and use.
Preferably, the softener is one or a mixture of more than two of polyethylene wax, paraffin oil, naphthenic oil and vaseline.
Preferably, the crosslinking agent is an organic peroxide or a metallic crosslinking agent. Preferably, the organic peroxide comprises one or two of dicumyl peroxide, bis 2, 4-dichlorobenzoyl peroxide; the metal organic compound comprises one or more of aluminum isopropoxide, zinc acetate and titanium acetylacetonate.
The organic peroxide or the metal crosslinking agent has certain crosslinking effect but is not violent in the system of the invention, the crosslinking strength is moderate, the rubber material is ensured to meet the requirement of use performance, and the water dissolving effect of the rubber material after use is not influenced.
Preferably, the accelerator consists of a mixture of 4: 1-2: 1 and a co-accelerator. Wherein, the vulcanization accelerator comprises one or two of an accelerator D or an accelerator M. In a preferred embodiment, the vulcanization accelerator is a combination accelerator consisting of accelerator D and accelerator M. Wherein, the accelerator D has a molecular formula of C13H13N3, and is mainly used as a medium-speed accelerator for natural rubber and synthetic rubber. And the chemical name of the accelerator M is 2-mercaptobenzothiazole, which is abbreviated as MBT. The auxiliary accelerator comprises one or two of zinc oxide or magnesium oxide.
The formula system of the invention is different from a single rubber system, has unique physical and chemical properties, and a plurality of rubber accelerators are not suitable for the system. Due to different activities and reaction speeds of various accelerators, the accelerator D and the accelerator M are screened out as the composite accelerator of the system through a large number of experiments, the water-soluble rubber with optimal target performance can be obtained by combining the accelerators, the processing reaction process is mild and controllable, and the performance meets the requirements. The co-promoter can shorten the reaction time, reduce the reaction temperature, is favorable for shortening the molding processing time, and has the function of preventing the product from being burnt.
The invention also provides a preparation method of the water-soluble rubber, which comprises the following specific steps:
s1, sequentially adding acrylamide modified polyurethane, carboxymethyl chitosan, a compatilizer, a coupling agent, an antioxidant and a softener in corresponding parts by weight into an internal mixer or an open mill, mixing for 20-40min at the blending temperature of 200-220 ℃, and standing for 25-35h to obtain a material 1;
s2, taking out the material 1, putting the material into granulation equipment for granulation or grinding the material into powder with the particle size of 300-1500 meshes to obtain a material 2;
s3, adding the material 2 into a mixer, sequentially adding the cross-linking agent, the accelerant and the sulfur in corresponding parts by weight, and stirring for 3-10min at the rotation speed of 300-800 rpm; and adding the mixed materials into a forming die, pressing into a product at the pressure of 5-25MPa and the temperature of 200-300 ℃ for 20-40min, and thus obtaining the water-soluble rubber.
The invention has the beneficial effects that:
1. the water-soluble rubber provided by the invention has the characteristics of the traditional elastomer rubber, and has the characteristics of swelling in water environment, performance attenuation or invalidation with time, dissolubility time controllability and the like. The material easy to hydrolyze is used as a matrix, the high-molecular elastomer chain segment is grafted and modified to ensure that the high-molecular elastomer chain segment has certain rubber elasticity and strength, the main chain has the characteristic of being dissolved in water, the added natural water-soluble material initiates the water-soluble disintegration of the material, the proportion of the material can be controlled to control the dissolution time and the strength retention rate, the dissolution in water is realized, a customized product is provided for customers in the military industry field and the petroleum field, and the high-molecular elastomer chain segment has high economic value and social value.
2. The water-soluble rubber provided by the invention is convenient to construct, high in dissolving efficiency and capable of reducing the construction cost. The rubber component has good application prospect and huge market, and can be widely used for temporary functional rubber components or products in oil field underground, tunnels, subways, culverts, underwater engineering, offshore oil extraction, civil buildings and the like.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items. In addition, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
1. The embodiment provides a water-soluble rubber which is mainly prepared from the following components in parts by mass:
55 parts of acrylamide modified polyurethane, 25 parts of carboxymethyl chitosan, 15 parts of polyvinyl alcohol grafted glycidyl methacrylate, 5 parts of maleic anhydride grafted SBS, 0.5 part of coupling agent, 0.5 part of antioxidant, 2.5 parts of softener, 0.5 part of crosslinking agent, 0.5 part of accelerator and 0.8 part of sulfur.
2. The embodiment provides a preparation method of water-soluble rubber, which comprises the following specific steps:
step one, adding 55 parts of acrylamide modified polyurethane, 25 parts of carboxymethyl chitosan, 15 parts of polyvinyl alcohol grafted glycidyl methacrylate, 5 parts of maleic anhydride grafted SBS, 0.5 part of coupling agent, 0.5 part of antioxidant and 2.5 parts of softener in an internal mixer or an open mill in sequence, mixing for 30 minutes at the blending temperature of 210 ℃, and standing for 30 hours to obtain a material 1;
taking the material 1 out of the internal mixer or the open mill, granulating in a granulating device or grinding in a grinding device into powder with the particle size of 500 meshes to obtain a material 2;
step three, adding the material 2 into a high-speed mixer, rotating at the speed of 400rpm, then sequentially adding 0.5 part of cross-linking agent, 0.5 part of accelerant and 0.8 part of sulfur, and stirring for 5 minutes; adding the mixed materials into a forming die, pressing for 30min at the pressure of 15MPa and the temperature of 180 ℃, and forming into the required product.
Example 2
1. The embodiment provides a water-soluble rubber which is mainly prepared from the following components in parts by mass:
55 parts of acrylamide modified polyurethane, 25 parts of carboxymethyl chitosan, 5 parts of polyvinyl alcohol grafted glycidyl methacrylate, 5 parts of maleic anhydride grafted SBS, 0.5 part of coupling agent, 0.5 part of antioxidant, 2.5 parts of softener, 0.5 part of crosslinking agent, 0.5 part of accelerator and 0.8 part of sulfur.
2. The embodiment also provides a preparation method of the water-soluble rubber, which comprises the following specific steps:
step one, adding 55 parts of acrylamide modified polyurethane, 25 parts of carboxymethyl chitosan, 5 parts of polyvinyl alcohol grafted glycidyl methacrylate, 5 parts of maleic anhydride grafted SBS, 0.5 part of coupling agent, 0.5 part of antioxidant and 2.5 parts of softener in an internal mixer or an open mill in sequence, mixing for 30 minutes at the blending temperature of 210 ℃, and standing for 30 hours to obtain a material 1;
taking the material 1 out of the internal mixer or the open mill, granulating in a granulating device or grinding in a grinding device into powder with the particle size of 1000 meshes to obtain a material 2;
step three, adding the material 2 into a high-speed mixer, rotating at the speed of 400rpm, then sequentially adding 0.5 part of cross-linking agent, 0.5 part of accelerant and 0.8 part of sulfur, and stirring for 5 minutes; adding the mixed materials into a forming die, pressing under the pressure of 15MPa and at the temperature of 200 ℃ for 20min to obtain the required product.
Example 3
1. The embodiment provides a water-soluble rubber which is mainly prepared from the following components in parts by mass:
35 parts of acrylamide modified polyurethane, 30 parts of carboxymethyl chitosan, 20 parts of polyvinyl alcohol grafted glycidyl methacrylate, 10 parts of maleic anhydride graft, 0.8 part of coupling agent, 0.6 part of antioxidant, 2.5 parts of softener, 0.5 part of crosslinking agent, 0.5 part of accelerator and 0.8 part of sulfur.
2. The embodiment provides a preparation method of the water-soluble rubber, which comprises the following specific steps:
step one, adding 35 parts of acrylamide modified polyurethane, 30 parts of carboxymethyl chitosan, 20 parts of polyvinyl alcohol grafted glycidyl methacrylate, 10 parts of maleic anhydride grafted SBS, 0.8 part of coupling agent, 0.6 part of antioxidant and 2.5 parts of softener in an internal mixer or an open mill in sequence, mixing for 30 minutes at the blending temperature of 210 ℃, and standing for 30 hours to obtain a material 1;
and step two, taking the material 1 out of the internal mixer or the open mill, granulating in a granulating device or grinding in a grinding device into powder with the particle size of 300 meshes, and obtaining a material 2.
Step three, adding the material 2 into a high-speed mixer, rotating at the speed of 400rpm, then sequentially adding 0.5 part of cross-linking agent, 0.5 part of accelerant and 0.8 part of sulfur, and stirring for 5 minutes; adding the mixed materials into a forming die, pressing under the pressure of 15MPa and at the temperature of 180 ℃ for 20min to obtain the required product.
Comparative example 1
This example provides a method for preparing a water-soluble rubber as a comparative example, which comprises the following steps:
step one, adding 70 parts of common natural rubber, 5 parts of butadiene rubber, 10 parts of polyvinyl alcohol grafted glycidyl methacrylate, 5 parts of maleic anhydride grafted SBS, 10 parts of silicon dioxide, 0.5 part of coupling agent, 0.5 part of antioxidant and 2.5 parts of softener into an internal mixer or an open mill in sequence, mixing for 30 minutes at the blending temperature of 30 ℃, and standing for 30 hours to obtain a material 1;
and step two, taking the material 1 out of the internal mixer or the open mill, granulating in a granulating device or grinding in a grinding device into powder with the particle size of 150 meshes, and obtaining a material 2.
Step three, adding the material 2 into a high-speed mixer, rotating at the speed of 400rpm, then sequentially adding 0.5 part of cross-linking agent, 0.5 part of accelerant and 0.8 part of sulfur, and stirring for 5 minutes; adding the mixed materials into a forming die, pressing under the pressure of 15MPa and at the temperature of 180 ℃ for 20min to obtain the required product.
EXAMPLE 4 Performance testing of Water-soluble rubbers
The water-soluble rubbers prepared in examples 1 to 3 and comparative example 1 were divided into 4 groups, and each group was subjected to the following performance tests, wherein the test method of the solubility performance was an enterprise standard method:
and taking a material sample piece with the thickness of 100mm x 2mm, and recording the relation between the weight loss of the sample and the time in high-pressure high-temperature water at the temperature of 70-120 ℃. The time at which the sample weight loss reached 50% wt was taken as the dissolution behavior of the material: the shorter the time, the more soluble the material is at the same temperature; the longer the time, the poorer the dissolution properties of the material.
The results of the testing of the water soluble rubbers are given in the following table:
according to the test data, the water-soluble rubber prepared in the examples 1-3 is superior to the comparative example material in the aspects of mechanical strength and solubility, and is superior to or equal to the comparative example value in the aspects of temperature resistance, density, thermal aging performance and the like.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. The water-soluble rubber is characterized by being mainly prepared from the following components in parts by weight:
35-55 parts of acrylamide modified polyurethane (AM-PU), 20-30 parts of carboxymethyl chitosan, 5-40 parts of compatilizer, 0.3-2 parts of coupling agent, 0.1-1 part of antioxidant, 1-5 parts of softener, 0.3-3 parts of crosslinking agent, 0.3-3 parts of accelerator and 0.5-6 parts of sulfur; the mass ratio of the accelerator is 4: 1-2: 1, the vulcanization accelerator is a composite accelerator consisting of an accelerator D and an accelerator M; the crosslinking agent includes an organic peroxide or a metal organic compound.
2. The water-soluble rubber according to claim 1, wherein the compatibilizer is one or more of polyvinyl alcohol grafted glycidyl methacrylate (PVA-g-GMA), maleic anhydride grafted SBS, and maleic anhydride grafted SEBS.
3. The water-soluble rubber according to claim 1, wherein the number average molecular weight of the acrylamide-modified polyurethane is 0.5 to 6.5 ten thousand.
4. The water-soluble rubber according to claim 1, wherein the carboxymethyl chitosan is granular or powder with a mesh size of 300-1500 meshes.
5. The water-soluble rubber according to claim 1, wherein the organic peroxide comprises one or both of dicumyl peroxide, bis 2, 4-dichlorobenzoyl peroxide; the metal organic compound comprises one or more of aluminum isopropoxide, zinc acetate and titanium acetylacetonate.
6. The water-soluble rubber according to claim 1, wherein the co-accelerator comprises one or both of zinc oxide and magnesium oxide.
7. The water-soluble rubber according to claim 1, wherein the antioxidant consists of 1010, 168 and HP-136 in a weight ratio of 1:1.5: 1.
8. The water-soluble rubber according to claim 1, wherein the softener is one or a mixture of two or more of polyethylene wax, paraffin oil, naphthenic oil and vaseline.
9. A method for preparing water-soluble rubber according to any one of claims 1 to 8, comprising the following steps:
s1, sequentially adding acrylamide modified polyurethane, carboxymethyl chitosan, a compatilizer, a coupling agent, an antioxidant and a softener in corresponding parts by weight into an internal mixer or an open mill, mixing for 20-40min at the blending temperature of 200-220 ℃, and standing for 25-35h to obtain a material 1;
s2, taking out the material 1, putting the material into granulation equipment for granulation or grinding the material into powder with the particle size of 300-1500 meshes to obtain a material 2;
s3, adding the material 2 into a mixer, sequentially adding the cross-linking agent, the accelerant and the sulfur in corresponding parts by weight, and stirring for 3-10min at the rotation speed of 300-800 rpm; and adding the mixed materials into a forming die, pressing the materials into a product at the pressure of 5-25MPa and the temperature of 180 ℃ and 250 ℃ for 20-40min, and thus obtaining the water-soluble rubber.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3652747A (en) * | 1969-03-17 | 1972-03-28 | Dainippon Ink & Chemicals | Process for manufacturing synthetic leather |
| CN1289359A (en) * | 1998-01-09 | 2001-03-28 | 达特韦勒橡胶塑料股份公司 | Sealing Material which swells when treated with water |
| CN104246115A (en) * | 2012-04-16 | 2014-12-24 | 瑞翁化工公司 | High temperature stable water swellable rubber composition |
| CN106030023A (en) * | 2014-03-07 | 2016-10-12 | 株式会社吴羽 | Degradable rubber member for downhole tool, degradable seal member, degradable protective member, downhole tool, and well-drilling method |
| CN108623781A (en) * | 2018-05-18 | 2018-10-09 | 南京宜凯瑞新材料有限公司 | A kind of synthesis technology of aqueous polyurethane |
-
2018
- 2018-12-29 CN CN201811638950.1A patent/CN109810451B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3652747A (en) * | 1969-03-17 | 1972-03-28 | Dainippon Ink & Chemicals | Process for manufacturing synthetic leather |
| CN1289359A (en) * | 1998-01-09 | 2001-03-28 | 达特韦勒橡胶塑料股份公司 | Sealing Material which swells when treated with water |
| CN104246115A (en) * | 2012-04-16 | 2014-12-24 | 瑞翁化工公司 | High temperature stable water swellable rubber composition |
| CN106030023A (en) * | 2014-03-07 | 2016-10-12 | 株式会社吴羽 | Degradable rubber member for downhole tool, degradable seal member, degradable protective member, downhole tool, and well-drilling method |
| CN108623781A (en) * | 2018-05-18 | 2018-10-09 | 南京宜凯瑞新材料有限公司 | A kind of synthesis technology of aqueous polyurethane |
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