CN111423630A - Rubber mixture for cleaning self-adhesive mold, preparation method and use method thereof - Google Patents

Rubber mixture for cleaning self-adhesive mold, preparation method and use method thereof Download PDF

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Publication number
CN111423630A
CN111423630A CN202010326720.2A CN202010326720A CN111423630A CN 111423630 A CN111423630 A CN 111423630A CN 202010326720 A CN202010326720 A CN 202010326720A CN 111423630 A CN111423630 A CN 111423630A
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rubber mixture
rubber
polybutadiene
temperature
mixing
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Inventor
刘韬
钱寒东
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Jiangsu Tokan New Material Co ltd
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Jiangsu Tokan New Material Co ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00Compositions of natural rubber
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00Mixing; Kneading
    • B29B7/002Methods
    • B29B7/005Methods for mixing in batches
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00Mixing; Kneading
    • B29B7/002Methods
    • B29B7/007Methods for continuous mixing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00Moulds or cores; Details thereof or accessories therefor
    • B29C33/70Maintenance
    • B29C33/72Cleaning
    • B29C33/722Compositions for cleaning moulds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/17Component parts, details or accessories; Auxiliary operations
    • B29C45/1753Cleaning or purging, e.g. of the injection unit
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2237Oxides; Hydroxides of metals of titanium
    • C08K2003/2241Titanium dioxide
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2296Oxides; Hydroxides of metals of zinc
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

A self-adhesive rubber mixture for cleaning a mold, a preparation method and a use method thereof relate to the technical field of production of composite materials and cleaning of molds. Plasticating NR and 1, 2-polybutadiene in an internal mixer, adding white carbon black, titanium dioxide, zinc oxide, triethanolamine, a plasticizer and petroleum resin after the material temperature reaches 180 ℃, mixing again, standing and cooling the mixed material obtained after mixing to room temperature, placing on an open mill for cooling, dispersing and mixing, simultaneously adding a vulcanizing agent and an accelerator, mixing uniformly, thinning and slicing, and cooling the sheet to obtain the rubber mixture. The rubber mixture is placed in a mold cavity for vulcanization or injection molding, and the mold is cleaned. The material has good compatibility with rubber, can increase the strength of a cross-linking material, has certain viscosity at high temperature, and is favorable for adsorbing impurities in a high-temperature and high-pressure die cavity.

Description

Rubber mixture for cleaning self-adhesive mold, preparation method and use method thereof
Technical Field
The invention relates to the technical field of composite material production and also relates to the technical field of mold cleaning.
Background
In the production process of rubber and plastic products, a large number of metal molds are used, and because the high-molecular products are easily decomposed at high temperature and high pressure to generate low-molecular pollutants, small parts of the pollutants can be adhered to the metal molds, and on the other hand, moisture in the air can also react with the metal molds to generate rust and the like, the molds can be seriously polluted in the use or parking process in a long-term process, so that qualified products cannot be produced, and the product quality is influenced. The traditional mode of washing the mould is with the mould cooling, and the manual work is pulled out from the machine, puts to spacious place, washs with acid solution, has washd, installs on equipment after the sunning.
The traditional method has two serious problems, on one hand, the acidic solvent is used, waste liquid is generated, and the environmental hazard is great; on the other hand, the mold needs to be cooled, disassembled and assembled, and long working hours are needed, so that the influence on production is serious, and the efficiency is low.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention provides a self-adhesive rubber composition for mold cleaning that can be conveniently used for cleaning molds.
The invention mainly comprises NR (natural rubber), 1, 2-polybutadiene, white carbon black, titanium dioxide, zinc oxide, triethanolamine, 1, 2-ethylene glycol, naphthenic oil, petroleum resin, sulfur and an accelerant.
The invention uses NR (natural rubber) and 1, 2-polybutadiene as main materials, and combines petroleum resin capable of increasing viscosity and amine compound capable of reacting with metal ions such as rust, and then combines with a vulcanization crosslinking system. The material can be directly used on a mould using device, various impurity pollutants on the surface of the mould are reacted and adhered under high pressure and high temperature, and the material and the adhered impurities are solidified into a whole together after a certain time at high temperature and high pressure by utilizing the thermosetting characteristic of rubber, so that the material can be easily removed after mould opening.
The 1, 2-polybutadiene can increase the adhesive property of sizing materials and improve the adhesive effect on metal surfaces, the naphthenic oil also has the effects of reducing the hardness, increasing the fluidity of the sizing materials and improving the adsorption effect, and the 1, 2-ethylene glycol can adjust the acidity and alkalinity of the whole mixture to increase the crosslinking density of the materials, thereby being beneficial to the effect of opening the molds and demoulding.
Furthermore, the weight mixing ratio of the NR (natural rubber), the 1, 2-polybutadiene, the white carbon black, the titanium dioxide, the zinc oxide, the triethanolamine, the 1, 2-ethylene glycol, the naphthenic oil, the petroleum resin, the sulfur and the accelerator is 70-80: 30-20: 20-30: 3-5: 10-20: 2-4: 10-20: 5-10: 0.6-1.0.
The invention takes the natural rubber as the main base material, on one hand, the price is lower, on the other hand, the natural rubber can be crosslinked, and the vulcanization speed is higher; the 1, 2-polybutadiene is matched with natural rubber, so that the compatibility is good, the self-adhesion is good, and the material has good adsorption effect; the triethanolamine has a good cleaning effect and can react with impurities such as the rust in the die cavity and the like to remove stubborn surface dirt. The petroleum resin and the naphthenic oil can improve the viscosity of the material and are beneficial to the processing performance of the material. The other materials are basically matched with rubber materials, so that the materials can be quickly vulcanized and crosslinked at high temperature, the sulfide strength is also endowed, and the mixture can be easily taken out of a mold cavity.
A second object of the present invention is to propose a process for the preparation of the above cleaning rubber mixture.
The invention comprises the following steps:
1) plasticating NR and 1, 2-polybutadiene in an internal mixer for at least 10 minutes, feeding white carbon black, titanium dioxide, zinc oxide, triethanolamine, a plasticizer and petroleum resin into the internal mixer after the material temperature reaches 180 ℃, and then mixing for 12-20 minutes under the condition that the temperature is less than or equal to 120 ℃;
2) standing and cooling the mixed material obtained after mixing to room temperature, placing the mixed material on an open mill for cooling, dispersing and mixing, adding a vulcanizing agent and an accelerator, uniformly mixing, thinning and slicing, and cooling the slices to below 70 ℃ to obtain the rubber mixture.
In the step 1), the purpose of plasticating the NR and the 1, 2-polybutadiene is to utilize the thermal oxidation degradation to break the macromolecular chain of the 1, 2-polybutadiene and generate the micromolecular polybutene, so that the 1, 2-polybutadiene and the NR can be better mixed, and stronger viscosity is generated, so that the rubber has better effect on adhering impurities on the surface of a mold in the using process of a product. The mixing time after the white carbon black, the titanium white, the zinc oxide, the triethanolamine, the plasticizer and the petroleum resin are added is that partial low molecular weight liquid volatilizes at high temperature so that the obtained mixture loses partial viscosity; when the materials are uniformly mixed and have uniform color and no particles, the material can be discharged.
The vulcanizing agent and the accelerator are added in an open mill after the temperature of the material is reduced, and the vulcanizing agent and the accelerator are mainly used for preventing the material from being crosslinked in advance at high temperature, so that partial adhesiveness is lost, and the mold washing efficiency is reduced.
In the above step 2), the cooling time is usually at least 8 hours, and the temperature is not higher than 70 ℃ so as to avoid the premature crosslinking reaction inside the mixture when the vulcanization system is added.
In a word, through the above process, the purposes of uniform material mixing, uniform performance, high strength, difficult self-vulcanization and long retention period are realized.
In addition, the NR is 3L natural rubber, the Mooney viscosity is 60-90, and the natural rubber is easy to process and is beneficial to uniform dispersion of materials.
The Mooney viscosity of the 1, 2-polybutadiene is 60-90, the crystallinity is 50-70%, the melting temperature is 170-200 ℃, the compatibility with natural rubber is facilitated, and the 1, 2-polybutadiene has certain viscosity and strength.
The 1, 2-polybutadiene is syndiotactic 1, 2-polybutadiene synthesized by an iron catalyst. The syndiotactic 1, 2-polybutadiene synthesized by the method has high crystallinity, high melting temperature, high viscosity at high temperature and low viscosity at low temperature, and is beneficial to processing.
The petroleum resin is obtained by catalytic polymerization reaction of ethylene tar and carbon nine serving as raw materials, and the product is yellow, brown and blocky solid in appearance and has a softening point of 75-135 ℃. The material has good compatibility with rubber, can increase the strength of a cross-linking material, has certain viscosity at high temperature, and is favorable for adsorbing impurities in a high-temperature and high-pressure die cavity.
A third object of the invention is to propose two methods of use of the above rubber mixtures.
The first method is as follows: and adding the rubber mixture into a mold cavity, vulcanizing for 3-10 min on vulcanization equipment under the conditions that the pressure is 5-12 MPa and the temperature is 150-170 ℃ to crosslink dirt in the mold cavity and the rubber mixture into a solid mixture, opening the mold and taking out the solid mixture with the dirt, and finishing cleaning the metal mold cavity.
If the used equipment is a flat vulcanizing machine and a common mold, the rubber mixture is properly weighed according to the shape and size of the mold cavity of the mold, and by the method, dirt in the mold cavity is reacted or bonded in the rubber mixture and permeates into vulcanized colloid, and the solid mixture with the dirt is crosslinked at high temperature and high pressure, so that the impurity dirt is easily taken away, and the bright surface of the mold cavity of the mold is recovered; if the effect is insufficient, the rubber mixture can be repeatedly used in the above-mentioned manner.
The second method is as follows: and (3) performing extrusion molding on the rubber mixture in an injection molding machine under the conditions that the pressure is 5-12 MPa and the temperature is 150-170 ℃, and cleaning a mold cavity and a mold of the injection molding machine.
If the used equipment is rubber and plastic injection molding equipment and a mold, on one hand, the rubber mixture can be extruded in the injection molding machine for a long time or circularly by adopting the method, so that impurities and rust in the internal channel of the equipment are taken out by the rubber mixture, and the mold is bright; if the effect is insufficient, the material can be used for multiple operations by adopting the method.
Detailed Description
Firstly, preparing a cleaning rubber mixture:
1. preparing materials:
NR is 3L natural rubber, and the Mooney viscosity is 60-90.
The 1, 2-polybutadiene is syndiotactic 1, 2-polybutadiene synthesized by using an iron-based catalyst, and the Mooney viscosity of the 1, 2-polybutadiene is 60-90, the crystallinity is 50-70%, and the melting temperature is 170-200 ℃ as disclosed in the method of Z L2017105401007.
The petroleum resin is ethylene tar and carbon nine which are used as raw materials and are obtained by catalytic polymerization, the product is yellow, brown and blocky solid in appearance, and the softening point is 75-135 ℃.
2. Weighing table:
weighing the following ten formulas respectively:
Figure 554241DEST_PATH_IMAGE001
3. the process comprises the following steps:
(1) plasticating NR and 1, 2-polybutadiene in an internal mixer for at least 10 minutes, setting the rotating speed of the internal mixer to be 100 r/min, rapidly increasing the temperature along with the continuous friction between a rubber material and a cavity, opening an upper top bolt of the internal mixer after the material temperature reaches 180 ℃ and is stabilized for 1 minute, then adding white carbon black, titanium dioxide, zinc oxide, triethanolamine, a plasticizer and petroleum resin into the internal mixer, closing the upper top bolt, continuously mixing for 12-20 minutes under the condition that the temperature is less than or equal to 120 ℃, and opening a lower top bolt for discharging.
(2) Standing and cooling the mixed material obtained after mixing to room temperature, placing the mixed material on an open mill for cooling, dispersing and mixing, adding a vulcanizing agent and an accelerant, uniformly mixing, thinning and slicing, and cooling the slices to below 70 ℃ to obtain the mixed material.
4. The application comprises the following steps:
(1) and respectively putting the rubber mixtures respectively formed by the formula 1, the formula 2, the formula 3 and the formula 4 into a mold cavity, vulcanizing for 3-10 min on vulcanization equipment under the conditions of the pressure of 5-12 mPa and the temperature of 150-170 ℃, taking out the rubber mixtures from the mold, taking out the solid mixtures with dirt, and finishing cleaning a flat vulcanizing machine or a common mold. If the effect is insufficient, the rubber mixture can be repeatedly used in the above-mentioned manner.
(2) And respectively adding the rubber mixtures formed by the formula 5, the formula 6, the formula 7 and the formula 8 into an injection molding machine, and performing extrusion molding under the conditions of 5-12 MPa of pressure and 150-170 ℃ to complete cleaning of a mold cavity and a mold of the injection molding machine. If the effect is insufficient, the material can be used for multiple operations by adopting the method.
(3) And respectively adding the rubber mixtures respectively formed by the formula 1, the formula 2, the formula 9 and the formula 10 into a metal mold cavity, and vulcanizing for 3-10 min under the conditions that the pressure is 5-12 MPa and the temperature is 150-170 ℃, so that the dirt in the mold cavity and the rubber mixture are crosslinked into a solid mixture with the dirt, and the cleaning of the metal mold cavity is completed.

Claims (9)

1. A self-adhesive rubber mixture for cleaning moulds is characterized by mainly comprising NR, 1, 2-polybutadiene, white carbon black, titanium dioxide, zinc oxide, triethanolamine, 1, 2-ethylene glycol, naphthenic oil, petroleum resin, sulfur and an accelerator.
2. The rubber mixture according to claim 1, wherein the weight mixing ratio of the NR, the 1, 2-polybutadiene, the white carbon black, the titanium dioxide, the zinc oxide, the triethanolamine, the 1, 2-ethylene glycol, the naphthenic oil, the petroleum resin, the sulfur and the accelerator is 70-80: 30-20: 20-30: 3-5: 10-20: 2-4: 10-20: 5-10: 0.6-1.0.
3. A process for the preparation of a rubber mixture as claimed in claim 1 or 2, characterized in that it comprises the following steps:
1) plasticating NR and 1, 2-polybutadiene in an internal mixer for at least 10 minutes, feeding white carbon black, titanium dioxide, zinc oxide, triethanolamine, a plasticizer and petroleum resin into the internal mixer after the material temperature reaches 180 ℃, and then mixing for 12-20 minutes under the condition that the temperature is less than or equal to 120 ℃;
2) standing and cooling the mixed material obtained after mixing to room temperature, placing the mixed material on an open mill for cooling, dispersing and mixing, adding a vulcanizing agent and an accelerator, uniformly mixing, thinning and slicing, and cooling the slices to below 70 ℃ to obtain the rubber mixture.
4. The method for producing a rubber compound according to claim 3, wherein said NR is 3L natural rubber, and the Mooney viscosity is 60 to 90.
5. The method for producing a rubber compound according to claim 3, wherein the Mooney viscosity of the 1, 2-polybutadiene is 60 to 90, the crystallinity is 50 to 70%, and the melting temperature is 170 to 200 ℃.
6. The process for producing a rubber compound according to claim 5, wherein the 1, 2-polybutadiene is syndiotactic 1, 2-polybutadiene synthesized by using an iron-based catalyst.
7. The method for preparing a rubber mixture according to claim 3, wherein the petroleum resin is ethylene tar and carbon nine which are used as raw materials and are obtained by catalytic polymerization, and the product is yellow, brown and blocky solid in appearance and has a softening point of 75-135 ℃.
8. Method for using a rubber mixture according to claim 1, characterized in that: and adding the rubber mixture into a mold cavity, vulcanizing for 3-10 min on vulcanization equipment under the conditions that the pressure is 5-12 MPa and the temperature is 150-170 ℃ to enable dirt in the mold cavity and the rubber mixture to be crosslinked into solid, opening the mold and taking out the solid mixture with the dirt, and finishing cleaning the metal mold cavity.
9. Method for using a rubber mixture according to claim 1, characterized in that: and (3) performing extrusion molding on the rubber mixture in an injection molding machine under the conditions that the pressure is 5-12 MPa and the temperature is 150-170 ℃, and cleaning a mold cavity and a mold of the injection molding machine.
CN202010326720.2A 2020-04-23 2020-04-23 Rubber mixture for cleaning self-adhesive mold, preparation method and use method thereof Pending CN111423630A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115109327A (en) * 2022-08-22 2022-09-27 广东粤港澳大湾区黄埔材料研究院 Tire sidewall rubber composition and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1720126A (en) * 2002-12-06 2006-01-11 日本碳化物工业株式会社 Cleaning material for molding metal die, and cleaning method
CN101955858A (en) * 2009-07-17 2011-01-26 日东电工株式会社 Die cleaning agent composition and mould cleaning material and the mould cleaning method that uses it
CN103205032A (en) * 2013-03-14 2013-07-17 西北工业大学 Mold cleaning rubber for in-place mold cleaning and preparation method of mold cleaning rubber

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1720126A (en) * 2002-12-06 2006-01-11 日本碳化物工业株式会社 Cleaning material for molding metal die, and cleaning method
CN101955858A (en) * 2009-07-17 2011-01-26 日东电工株式会社 Die cleaning agent composition and mould cleaning material and the mould cleaning method that uses it
CN103205032A (en) * 2013-03-14 2013-07-17 西北工业大学 Mold cleaning rubber for in-place mold cleaning and preparation method of mold cleaning rubber

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115109327A (en) * 2022-08-22 2022-09-27 广东粤港澳大湾区黄埔材料研究院 Tire sidewall rubber composition and preparation method thereof
CN115109327B (en) * 2022-08-22 2022-11-18 广东粤港澳大湾区黄埔材料研究院 Tire sidewall rubber composition and preparation method thereof

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Application publication date: 20200717