CN111205520A - Micro-foaming ball for pet and manufacturing method thereof - Google Patents
Micro-foaming ball for pet and manufacturing method thereof Download PDFInfo
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- CN111205520A CN111205520A CN202010189593.6A CN202010189593A CN111205520A CN 111205520 A CN111205520 A CN 111205520A CN 202010189593 A CN202010189593 A CN 202010189593A CN 111205520 A CN111205520 A CN 111205520A
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/104—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/101—Agents modifying the decomposition temperature
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
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- C08K5/00—Use of organic ingredients
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Abstract
A micro-foaming ball for pets and a manufacturing method thereof relate to the technical field of production of composite materials, and are characterized in that NR, POE, carbon black, an anti-aging agent and a plasticizer are mixed and then are mixed by an internal mixer, and the mixture is discharged to obtain a mixed material; placing the mixed material on an open mill for cooling, dispersing and mixing, adding an OBSH modified foaming agent, a vulcanizing agent and an accelerant, uniformly mixing, thinning and slicing, and cooling to obtain a mixed material; and then preparing a smooth blank from the mixed material on an extruder through high shearing force, cutting the blank into a coarse blank, coating talcum powder on the coarse blank, then placing the coarse blank in a forming die, vulcanizing the coarse blank in a high-temperature vulcanizing agent, demoulding, cooling and trimming to obtain the high-temperature vulcanizing agent. The product of the invention has light hand feeling, good rebound resilience, bright color, good toughness and tearing property, smooth surface and high durability for pet biting.
Description
Technical Field
The invention relates to the technical field of composite material production.
Background
The ball for the pet produced by the traditional process is made of rubber materials singly, has the defects of poor toughness, low strength and easy generation of weak bubble holes on the surface, and is easy to damage the surface of the ball body through repeated biting. On the other hand, in the traditional production process of the pet ball, N-dinitrosopentamethylenetetramine (foaming agent H) is adopted, and after high-temperature vulcanization, residues of the foaming agent contain derivatives of nitro or nitroso, so that the foaming agent has certain toxicity and is harmful to pet bodies.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a micro-foaming ball for pets.
The invention mainly comprises NR, POE, carbon black, an anti-aging agent, a plasticizer, an OBSH modified foaming agent, a vulcanizing agent and an accelerator.
With the continuous development of rubber and plastic combined materials, the technology is mature day by day, natural rubber (namely NR) and polyethylene octene co-elastomer (POE for short) not only can keep the high elasticity and high strength of rubber, but also can have the toughness of POE, and through continuous experiments, the rubber and plastic combined material can be used for preparing products with smooth surfaces and uniform internal foaming in the field of micro-foaming materials. In addition, the technical problems of product surface cracking, internal sphere layering and the like caused by the contradiction that the foaming temperature of the 4, 4-oxo-diphenyl sulfonyl hydrazide is too high and the heat conduction efficiency of the rubber plastic material is low due to the wall thickness of a sphere product can be solved through the matching of various materials. According to the invention, the foaming temperature of the OBSH modified foaming agent is reduced by introducing materials such as urea and the like to prepare the modified foaming agent, the characteristics of uniform foaming, low shrinkage rate and the like of the foaming agent are kept, and more importantly, the residues of the OBSH foaming agent are non-toxic and harmless. On the other hand, the invention adopts the cooperation of a vulcanization system, reduces the crosslinking speed of the rubber-plastic main body, and ensures that the crosslinking speed is matched with the foaming speed, thereby preparing the sphere with uniform internal and external foaming and smooth and non-cracking surface. The prepared ball has the characteristics of good elasticity, strong toughness, smooth surface and bright color, can attract the pet to play, and is resistant to the bite of the pet.
In a word, the ball body which is light in hand feeling, good in rebound resilience, bright in color, good in toughness and tearing property and smooth in surface, can attract the pet to play and is high in durability in actions of being suitable for biting of the pet and the like is prepared by mechanically blending the natural rubber and the polyethylene octene co-elastomer, performing vulcanization crosslinking and performing high-temperature catalytic foaming.
Furthermore, the weight ratio of NR, POE, carbon black, an anti-aging agent, a plasticizer, an OBSH modified foaming agent, a vulcanizing agent and an accelerator is 50-60: 10-20: 20-30: 0.6-1.0: 10-15: 1.5-2.5: 0.6-1.0.
The invention takes NR as a main material to keep the elasticity and the mechanical strength of the material, and the toughness of the product can be enhanced by matching POE with a certain weight ratio, and the addition of POE is beneficial to the smoothness and the integrity of the surface of the product through repeated tests. In addition, the proportion of the vulcanizing agent and the accelerator can ensure that the foaming speed and the vulcanizing speed are matched with each other in the high-temperature vulcanizing process, so that the problems of edge rot, large bubbles, uneven foaming and the like of a vulcanized product are solved.
In addition, the NR is 20# standard rubber, and the Mooney viscosity of the rubber is 80-110. The natural rubber adopting the parameters can enable the product to have higher mechanical strength and elasticity, and meanwhile, the Mooney viscosity can control the size uniformity of foaming to a certain extent after proportioning.
The POE has a melting point of 60-70 ℃ and a 100% modulus of 3.0-5.0 MPa. The polyethylene octene co-elastomer with the parameters has good toughness, no toxicity and harm, low softening point, and is beneficial to processing, and meanwhile, the polyethylene octene co-elastomer has good effects of improving the durability and the surface smoothness of products.
The invention also aims to provide a preparation method of the micro-foaming pet ball.
The invention comprises the following steps:
1) mixing NR, POE, carbon black, an anti-aging agent and a plasticizer, then mixing for 12-20 min by an internal mixer, and discharging at 110-120 ℃ to obtain a mixed material;
2) placing the mixed material on an open mill for cooling, dispersing and mixing, adding an OBSH modified foaming agent, a vulcanizing agent and an accelerant, uniformly mixing, thinning and slicing, and cooling for at least 8 hours to obtain a mixed material;
3) preparing a smooth blank from the mixed material on an extruder by high shearing force;
4) cutting the blank into rough blanks, coating talcum powder, placing the rough blanks into a forming die, vulcanizing the rough blanks in a high-temperature vulcanizing agent, demoulding, cooling and trimming to obtain the micro-foamed ball for the pet.
The invention has simple and reasonable process, is beneficial to production and has good stability of the prepared product. In addition, the process also has the following characteristics:
1. rubber and plastic are used together, and the rubber and the plastic are blended by a high-temperature banburying process.
2. The foaming auxiliary agent is adopted to reduce the foaming critical temperature of the foaming agent.
3. Through reasonable matching, the foaming temperature and the vulcanization temperature are matched to achieve uniform foaming and no surface fracture.
4. The blank forming process is made by extrusion.
Further, the weight ratio of the NR, the POE, the carbon black, the anti-aging agent, the plasticizer, the OBSH modified foaming agent, the vulcanizing agent and the accelerator is 50-60: 10-20: 20-30: 0.6-1.0: 10-15: 1.5-2.5: 0.6-1.0.
The preparation method of the OBSH modified foaming agent comprises the following steps: 4, 4-oxo-bis-benzenesulfonyl hydrazide, zinc stearate and urea are mixed according to the weight ratio of 5: 1: 1.5, and then the mixture is stirred at a high speed and uniformly dispersed to obtain the product. Here, adopt urea and zinc stearate as catalytic material, can effectively reduce foaming agent OBSH's critical foaming temperature, do benefit to whole material foaming speed and vulcanization speed's cooperation in high temperature vulcanization process, the foaming is too fast produces macropore or surface perforation easily, and the foaming is too slow easy local closely knit, and is inhomogeneous, and the proportion is too big.
The granularity of the 4, 4-oxo-bis-benzenesulfonyl hydrazide adopted in the preparation of the OBSH modified foaming agent is 1000-2000 meshes. For example, the particle size of 4, 4-oxybis-benzenesulfonyl hydrazide is too large, so that the surface is easy to foam, the surface strength is too low, and the using effect is influenced. For example, if the particle size of 4, 4-oxybis-benzenesulfonyl hydrazide is too small, the mixture is not uniformly dispersed, the foaming inside the product is not uniform, the specific gravity is too large, and the hand feeling is affected.
The NR is 20# standard rubber, and the Mooney viscosity is 80-110; the POE has a melting point of 60-70 ℃ and a 100% modulus of 3.0-5.0 MPa.
And vulcanizing for 20 minutes at the temperature of 150-170 ℃. The design starting point of the vulcanization condition is as follows: on the one hand, the temperature needs to be controlled above the foaming critical point of the material, so that bubbles are generated in the molten state of the material. On the other hand, the vulcanization time needs to be matched with the vulcanization speed and the foaming speed of the material in order to achieve the optimal foaming state.
Detailed Description
Firstly, preparing an OBSH modified foaming agent:
1. weighing:
5kg of 4, 4-oxo-bis-benzenesulfonyl hydrazide with the granularity of 1000-2000 meshes, 1kg of zinc stearate and 1.5kg of urea are weighed respectively.
2. The preparation process comprises the following steps:
all the materials are put into a high-speed stirrer, and the rotating speed is not lower than 5000 r/min.
After 2-5 minutes, stopping the machine, and standing for 30 minutes until the material is settled.
After 0.5 hour, the cover is opened, the surface of the powder is observed by eyes to be uniform without impurities, and the powder is discharged for standby after uniform color.
3. The prepared OBSH modified foaming agent has the product characteristics and parameters as follows:
(1) white particles, uniform color.
(2) The foaming critical temperature is 150 ℃.
Secondly, manufacturing the ball for the pet:
1. the manufacturing steps are as follows:
(1) weighing the raw materials according to the formula examples.
(2) Fully mixing the components except the OBSH modified foaming agent, the vulcanizing agent and the accelerator, then mixing for 12-20 min by an internal mixer, and discharging at the temperature of 110-120 ℃.
(3) And (3) cooling, dispersing and mixing the material obtained in the step (2) on an open mill, adding an OBSH modified foaming agent, a vulcanizing agent and an accelerator, uniformly mixing, thinning and slicing, and cooling for at least 8 hours for substitution.
(4) And (4) preparing a smooth blank from the material obtained in the step (3) on an extruder by high shearing force.
(5) Cutting the blank obtained in the step (4) into a coarse blank according to the weight, and coating talcum powder.
(6) And (3) adding the rough blank prepared in the step (5) into a forming die, vulcanizing in a high-temperature vulcanizing agent for 20 minutes at the vulcanizing temperature of 150-170 ℃, demolding, cooling and trimming to obtain the ball for the foamed pet.
2. Weighing the formula and the corresponding performance and parameters of the prepared product:
in each formulation example, NR (natural rubber) is 20# standard rubber, and the Mooney viscosity is 80-110.
The POE (polyethylene octene co-elastomer) has a melting point of 60-70 ℃ and a 100% modulus of 3.0-5.0 MPa.
The following table shows the following weight units: phr.
3. The ball for soaking pets is characterized in that:
the surface of the sphere is smooth and has no cracks; the color may be various colors; the air tightness is 0.3-0.8 g/cm3。
The resilience is greater than 50%.
Claims (10)
1. A micro-foaming ball for pets is characterized by mainly comprising NR, POE, carbon black, an anti-aging agent, a plasticizer, an OBSH modified foaming agent, a vulcanizing agent and an accelerator.
2. The micro-foamed pet ball according to claim 1, wherein the weight ratio of NR, POE, carbon black, an anti-aging agent, a plasticizer, an OBSH-modifying foaming agent, a vulcanizing agent and an accelerator is 50-60: 10-20: 20-30: 0.6-1.0: 10-15: 1.5-2.5: 0.6-1.0.
3. The micro-foamed pet ball according to claim 1 or 2, wherein the NR is 20# standard gum and the mooney viscosity is 80 to 110.
4. The microcellular foamed pet ball according to claim 1 or 2, wherein the POE has a melting point of 60 to 70 ℃ and a 100% modulus of 3.0 to 5.0 MPa.
5. A method of making a micro-foamed pet ball according to claim 1, comprising the steps of:
1) mixing NR, POE, carbon black, an anti-aging agent and a plasticizer, then mixing for 12-20 min by an internal mixer, and discharging at 110-120 ℃ to obtain a mixed material;
2) placing the mixed material on an open mill for cooling, dispersing and mixing, adding an OBSH modified foaming agent, a vulcanizing agent and an accelerant, uniformly mixing, thinning and slicing, and cooling for at least 8 hours to obtain a mixed material;
3) preparing a smooth blank from the mixed material on an extruder by high shearing force;
4) cutting the blank into rough blanks, coating talcum powder, placing the rough blanks into a forming die, vulcanizing the rough blanks in a high-temperature vulcanizing agent, demoulding, cooling and trimming to obtain the micro-foamed ball for the pet.
6. The method for producing a micro-foamed pet ball according to claim 5, wherein the weight ratio of the NR, POE, carbon black, the anti-aging agent, the plasticizer, the OBSH modified foaming agent, the vulcanizing agent and the accelerator is 50-60: 10-20: 20-30: 0.6-1.0: 10-15: 1.5-2.5: 0.6-1.0.
7. The method for manufacturing the micro-foamed pet ball according to claim 5, wherein the OBSH modified foaming agent is prepared by the following steps: 4, 4-oxo-bis-benzenesulfonyl hydrazide, zinc stearate and urea are mixed according to the weight ratio of 5: 1: 1.5, and then the mixture is stirred at high speed and uniformly dispersed to prepare the product.
8. The microcellular pet beads according to claim 7, wherein the 4, 4-oxybis-benzenesulfonylhydrazide has a particle size of 1000 to 2000 mesh.
9. The method for manufacturing a micro-foamed pet ball according to claim 5, wherein the NR is 20# standard rubber, and the Mooney viscosity is 80 to 110; the POE has a melting point of 60-70 ℃ and a 100% modulus of 3.0-5.0 MPa.
10. The method for manufacturing a micro-foamed pet ball according to claim 5, wherein the micro-foamed pet ball is vulcanized for 20 minutes at a temperature of 150 to 170 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010189593.6A CN111205520A (en) | 2020-03-18 | 2020-03-18 | Micro-foaming ball for pet and manufacturing method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010189593.6A CN111205520A (en) | 2020-03-18 | 2020-03-18 | Micro-foaming ball for pet and manufacturing method thereof |
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| CN111205520A true CN111205520A (en) | 2020-05-29 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112225955A (en) * | 2020-10-19 | 2021-01-15 | 禾创高分子技术(广东)有限公司 | High-toughness anti-bite wear-resistant pet chew toy rubber compound and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005041913A (en) * | 2003-07-23 | 2005-02-17 | Mitsui Chemicals Inc | Olefin elastomer composition for foam and its use |
| CN102775652A (en) * | 2012-08-16 | 2012-11-14 | 株洲时代新材料科技股份有限公司 | Thermoplastic elastomer micropore foaming material and preparation method thereof |
| CN106519408A (en) * | 2016-10-08 | 2017-03-22 | 宁波高新区万盟新材料科技有限公司 | Environment-friendly foaming material taking OBSH as foaming agent and preparation method thereof |
| CN109320794A (en) * | 2018-09-25 | 2019-02-12 | 天长市富宝橡塑制品有限公司 | A kind of fire-resistant high-resiliency rubber ball for pet playing and preparation method thereof |
-
2020
- 2020-03-18 CN CN202010189593.6A patent/CN111205520A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005041913A (en) * | 2003-07-23 | 2005-02-17 | Mitsui Chemicals Inc | Olefin elastomer composition for foam and its use |
| CN102775652A (en) * | 2012-08-16 | 2012-11-14 | 株洲时代新材料科技股份有限公司 | Thermoplastic elastomer micropore foaming material and preparation method thereof |
| CN106519408A (en) * | 2016-10-08 | 2017-03-22 | 宁波高新区万盟新材料科技有限公司 | Environment-friendly foaming material taking OBSH as foaming agent and preparation method thereof |
| CN109320794A (en) * | 2018-09-25 | 2019-02-12 | 天长市富宝橡塑制品有限公司 | A kind of fire-resistant high-resiliency rubber ball for pet playing and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112225955A (en) * | 2020-10-19 | 2021-01-15 | 禾创高分子技术(广东)有限公司 | High-toughness anti-bite wear-resistant pet chew toy rubber compound and preparation method thereof |
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