CN113121881A - Density-reducing and hardness-increasing filler for latex foam products, preparation method and application thereof - Google Patents
Density-reducing and hardness-increasing filler for latex foam products, preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/28—Glass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08J9/0066—Use of inorganic compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08J9/30—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by mixing gases into liquid compositions or plastisols, e.g. frothing with air
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2307/00—Characterised by the use of natural rubber
- C08J2307/02—Latex
Abstract
The invention relates to the latex foaming field, and provides a density-reducing and hardening filler for latex foaming products, which is a hollow glass bead fragment dispersion containing 40-50% of solid content, aiming at the problem that the hardness and density of natural latex foaming products are difficult to balance. The hollow glass microsphere fragments are used as the filler of the latex foaming product, and play roles in hardening and reducing density; the spherical hollow glass beads are ground to obtain glass fragments with arc-shaped lamellar structures, and the glass fragments are mutually wound with a reticular structure in a latex foaming product to play a role in hardening. The invention also provides a preparation method and application of the density-reducing and hardness-increasing filler for the latex foaming product.
Description
Technical Field
The invention relates to the field of latex foaming, in particular to a density-reducing and hardness-increasing filler for a latex foaming product, a preparation method and application thereof.
Background
Latex foamed articles are low density, porous, open-cell materials, which can also be said to be continuous foams of rubber. The latex foaming product has excellent buffering and pressure reducing performance, compression fatigue resistance, good heat preservation and sound insulation performance, good heat resistance and the like. Foamed products prepared from natural latex are popular among consumers because of their natural environmental protection, anti-mite property, and excellent physical properties.
The density of the natural latex foaming products produced in the industry is generally 75-100 kg-m3And the indentation hardness is between 80 and 140N. From the feedback of consumers, the product with indentation hardness of more than 120N is suitable and has better support, but the density of the product corresponding to the indentation hardness of more than 120N is generally 85kg/m3Left and right. Manufacturers are involved in a contradiction, and increasing the hardness inevitably increases the density, so that the cost is inevitably increased, and the competitiveness is reduced. To solve this problem, a certain amount of synthetic latex may be added to natural latex, but synthetic latex is generally smelly and is not environmentally friendly. Attempts have also been made to add inorganic fillers such as aluminum hydroxide, silica, talc, etc., to provide a stiffening effect. For example, a chinese patent publication No. CN102361736A, discloses a method of manufacturing a hard latex and a hard latex, mentions that hard particles such as particles made of silica or silica-containing nanocomposites can be added to the latex to increase the hardness of the coating, but these powders are all in a free state in the foam, cannot form effective links, and have limited effect of hardening. Accordingly, an ideal solution is needed.
Disclosure of Invention
The invention provides a density-reducing and hardening filler for latex foam products, aiming at overcoming the problem that the hardness and the density of natural latex foam products are difficult to balance, wherein hollow glass microsphere fragments are used as the filler of the latex foam products and play roles in hardening and reducing the density.
In order to achieve the purpose, the invention adopts the following technical scheme:
a density-reducing and hardening filler for latex foaming products is a dispersion of hollow glass microsphere fragments with a solid content of 40-50%.
The hollow glass microspheres are artificial pure white hollow glass microspheres/beads, belong to novel ultra-light filling materials, and the utilization of the hollow glass microspheres in the prior art is mostly based on a series of advantages brought by the spherical closed characteristics of the hollow glass microspheres, such as: the hollow glass microspheres are tiny round spheres and have good fluidity in liquid; the perfect sphere ensures that the spherical resin has the smallest specific surface area, so the oil absorption is low, the resin consumption is reduced, and meanwhile, the spherical resin has the function of increasing the fluidity of the resin and also reduces the resin consumption; the inside of the hollow glass microsphere is vacuum thin gas, and two different materials have density and heat conductivity coefficient difference, so that the hollow glass microsphere has the characteristics of sound insulation, heat insulation and low heat conduction.
But the invention creatively grinds the spherical hollow glass beads to obtain the glass fragments with the arc lamellar structure, compared with the conventional inorganic filler, the arc glass fragments can be intertwined with the reticular structure in the latex foaming product to form effective connection, thereby playing a role in hardening. Meanwhile, the characteristic of low density of the hollow glass microspheres is utilized, and the density can be reduced when the hollow glass microspheres are used for preparing latex foaming products. In addition, the hollow glass bead fragments are used for density reduction and hardening, so that the method has the advantages of safety, environmental protection and capability of reducing VOC.
Preferably, the dispersion comprises: 2-5 parts of potassium pyrophosphate, 1-3 parts of potassium oleate solution, 48-51 parts of water and hollow glass bead fragments by mass. The hollow glass microsphere contains some free metal ions, the stability of latex can be influenced when the hollow glass microsphere is subsequently used for preparing latex foaming products, and the stability of the latex after the hollow glass microsphere fragments are added is improved by adding potassium pyrophosphate and complexing the metal ions. The potassium oleate solution is used as a dispersant to prevent the mutual aggregation of hollow glass bead fragments, and can also play a role of a foaming agent when being subsequently used for preparing latex foaming products. The potassium oleate solution is preferably 20% by mass aqueous solution.
The invention also provides a preparation method of the filler, which comprises the steps of adding the potassium pyrophosphate solution and the potassium oleate solution into water, stirring for dissolving, adding the hollow glass beads, stirring uniformly, and grinding to obtain the filler.
Preferably, the density of the hollow glass beads is 30 to 50kg/m3。
Preferably, the grinding is carried out in a grinding tank, the rotating speed is 500-. The size of the hollow glass micro-beads can be adjusted by controlling the grinding rotating speed and the grinding time.
Preferably, the grinding tank is a vertical sanding tank.
The invention also provides the application of the filler, which comprises the steps of mixing 100 parts of natural latex, 4-7 parts of vulcanization package dispersoid, 2-5 parts of potassium oleate aqueous solution, 0.5-2 parts of potassium ricinoleate aqueous solution, 5-10 parts of the filler, 3-8 parts of zinc oxide and 0.5-2 parts of gelling agent by mass, curing for 6-12 hours in a water bath at the temperature of 28-40 ℃, foaming, shaping for 5-20 minutes by hot air, vulcanizing for 10-30 minutes in a steam box, and finally drying.
Preferably, the natural latex is high ammonia natural latex with solid content of 60%.
Preferably, the vulcanization package dispersion is sulfur, accelerator M and accelerator ZDC in a mass ratio of 2:1: 1.
Preferably, the solid content of the potassium oleate aqueous solution is 20%, and/or the solid content of the potassium ricinoleate is 35%, and/or the zinc oxide is 50% zinc oxide dispersion, and/or the gelling agent is 20% solid content sodium fluosilicate aqueous dispersion.
Therefore, the invention has the following beneficial effects: (1) the hollow glass microsphere fragments are used as the filler of the latex foaming product, and play roles in hardening and reducing density; the hollow glass microspheres are ultra-light filling materials, but are difficult to form effective connection with a foaming body, and the hardness improvement of a latex foaming product is very limited, the invention creatively grinds the spherical hollow glass microspheres to obtain glass fragments with arc lamellar structures, and the glass fragments are mutually wound with a reticular structure in the latex foaming product to play a hardening effect; (2) potassium pyrophosphate is added into the filler to complex metal ions of the hollow glass microsphere fragments, so that the stability of a system after the hollow glass microsphere fragments are added into latex is improved.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
In the present invention, unless otherwise specified, all the raw materials and equipment used are commercially available or commonly used in the art, and the methods in the examples are conventional in the art unless otherwise specified. In the following examples, the grinding tank is a vertical sanding tank; the potassium oleate solution is an aqueous solution with the mass fraction of 20%, the natural latex is high-ammonia natural latex with the solid content of 60%, the vulcanized bag dispersoid is sulfur, an accelerator M and an accelerator ZDC with the mass ratio of 2:1:1, the density of the hollow glass beads is 30-50kg/M3, the solid content of the potassium oleate aqueous solution is 20%, the solid content of potassium ricinoleate is 35%, zinc oxide is a zinc oxide dispersoid with the solid content of 50%, and the gelling agent is a sodium fluosilicate aqueous dispersion with the solid content of 20%.
Example 1
(1) Preparing a hollow glass bead fragment dispersion: firstly, adding 20g of potassium pyrophosphate and 20g of potassium oleate solution into 500g of water, stirring for dissolving, then adding 450g of hollow glass microspheres, and stirring for uniformly dispersing; adding the dispersion into a grinding tank, adding grinding beads with the volume of 1/4 of the grinding tank, grinding at the rotating speed of 500r/min for 30min to prepare a hollow glass bead fragment dispersion with the solid content of 45%;
(2) preparing a latex foamed product: 10kg of natural rubber latex, 0.7kg of a vulcanized rubber bag dispersion, 0.3kg of a potassium oleate aqueous solution, 0.1kg of a potassium ricinoleate aqueous solution, 0.5kg of a hollow glass bead fragment dispersion, 0.5kg of zinc oxide and 0.15kg of a gelling agent; curing the mixed latex in water bath at 30 ℃ for 12 hours, foaming, hot air shaping for 5 minutes, steam box vulcanizing for 30 minutes, and finally drying.
Example 2
(1) Preparing a hollow glass bead fragment dispersion: firstly, adding 20g of potassium pyrophosphate and 20g of potassium oleate solution into 500g of water, stirring for dissolving, then adding 450g of hollow glass microspheres, and stirring for uniformly dispersing; adding the dispersion into a grinding tank, adding grinding beads with the volume of 1/4 of the grinding tank, rotating at 800r/min, and grinding for 30min to prepare a hollow glass bead fragment dispersion with the solid content of 45%;
(2) preparing a latex foamed product: 10kg of natural rubber latex, 0.7kg of the vulcanized rubber latex, 0.3kg of the aqueous solution of potassium oleate, 0.1kg of the aqueous solution of potassium ricinoleate, 0.5kg of the dispersion of hollow glass bead fragments, 0.5kg of zinc oxide and 0.15kg of the gelling agent were mixed. Curing the mixed latex in water bath at 30 ℃ for 12 hours, foaming, hot air shaping for 5 minutes, steam box vulcanizing for 30 minutes, and finally drying.
Example 3
(1) Preparing a hollow glass bead fragment dispersion: firstly, 20g of potassium pyrophosphate and 20g of potassium oleate solution are added into 500g of water, stirred and dissolved, then 450g of hollow glass microspheres are added, and stirred and dispersed uniformly. Adding the dispersion into a grinding tank, adding grinding beads with the volume of 1/4 of the grinding tank, rotating at 500r/min, and grinding for 50min to prepare a hollow glass bead fragment dispersion with the solid content of 45%;
(2) preparing a latex foamed product: 10kg of natural rubber latex, 0.7kg of the vulcanized rubber latex, 0.3kg of the aqueous solution of potassium oleate, 0.1kg of the aqueous solution of potassium ricinoleate, 0.5kg of the dispersion of hollow glass bead fragments, 0.5kg of zinc oxide and 0.15kg of the gelling agent were mixed. Curing the mixed latex in water bath at 30 ℃ for 12 hours, foaming, hot air shaping for 5 minutes, steam box vulcanizing for 30 minutes, and finally drying.
Example 4
(1) Preparing a hollow glass bead fragment dispersion: firstly, 20g of potassium pyrophosphate and 20g of potassium oleate solution are added into 500g of water, stirred and dissolved, then 450g of hollow glass microspheres are added, and stirred and dispersed uniformly. Adding the dispersion into a grinding tank, adding grinding beads with the volume of 1/4 of the grinding tank, grinding at the rotating speed of 500r/min for 30min to prepare a hollow glass bead fragment dispersion with the solid content of 45%;
(2) preparing a latex foamed product: 10kg of natural rubber latex, 0.7kg of a vulcanized rubber latex, 0.3kg of an aqueous solution of potassium oleate, 0.1kg of an aqueous solution of potassium ricinoleate, 1kg of a dispersion of hollow glass bead fragments, 0.5kg of zinc oxide and 0.15kg of a gelling agent were mixed. Curing the mixed latex in water bath at 30 ℃ for 12 hours, foaming, hot air shaping for 5 minutes, steam box vulcanizing for 30 minutes, and finally drying.
Example 5
(1) Preparing a hollow glass bead fragment dispersion: adding 20g of potassium oleate solution 450g of hollow glass microspheres into 500g of water, and uniformly stirring and dispersing; adding the dispersion into a grinding tank, adding grinding beads with the volume of 1/4 of the grinding tank, grinding at the rotating speed of 500r/min for 30min to prepare a hollow glass bead fragment dispersion;
(2) the same as in example 1.
Example 6
(1) Preparation of hollow glass microbead fragment Dispersion
Firstly, 30g of potassium pyrophosphate and 10g of potassium oleate solution are added into 480g of water, stirred and dissolved, then 450g of hollow glass microspheres are added, and stirred and dispersed uniformly. Adding the dispersion into a grinding tank, adding grinding beads with the volume of 1/4 of the grinding tank, grinding at the rotating speed of 2000r/min for 20min to prepare a hollow glass bead fragment dispersion with the solid content of 40%;
(2) preparation of latex foamed articles
10kg of natural rubber latex, 0.5kg of the vulcanized rubber latex, 0.2kg of the aqueous solution of potassium oleate, 0.05kg of the aqueous solution of potassium ricinoleate, 0.8kg of the dispersion of hollow glass bead fragments, 0.3kg of zinc oxide and 0.05kg of the gelling agent were mixed. Curing the mixed latex in water bath at 28 ℃ for 10 hours, foaming, hot air shaping for 20 minutes, steam box vulcanizing for 10 minutes, and finally drying.
Example 7
(1) Preparation of hollow glass microbead fragment Dispersion
Firstly, 50g of potassium pyrophosphate and 30g of potassium oleate solution are added into 510g of water, stirred and dissolved, then 450g of hollow glass microspheres are added, and stirred and dispersed uniformly. Adding the dispersion into a grinding tank, adding grinding beads with the volume of 1/4 of the grinding tank, rotating at 800r/min, and grinding for 20min to prepare a hollow glass bead fragment dispersion with the solid content of 50%;
(2) preparation of latex foamed articles
10kg of natural rubber latex, 0.4kg of the vulcanized rubber latex, 0.5kg of the aqueous solution of potassium oleate, 0.2kg of the aqueous solution of potassium ricinoleate, 0.5kg of the dispersion of hollow glass bead fragments, 0.8kg of zinc oxide and 0.2kg of the gelling agent were mixed. The latex is matched to be aged for 6 hours in water bath at the temperature of 40 ℃, foamed, shaped by hot air for 10 minutes, vulcanized in a steam box for 20 minutes and finally dried.
Comparative example 1
(1) Preparing a hollow glass bead dispersion: firstly, adding 20g of potassium pyrophosphate and 20g of potassium oleate solution into 500g of water, stirring for dissolving, then adding 450g of hollow glass microspheres, and uniformly stirring and dispersing to prepare a hollow glass microsphere dispersion;
(2) preparing a latex foamed product: 10kg of natural rubber latex, 0.7kg of a vulcanized rubber latex, 0.3kg of a potassium oleate aqueous solution, 0.1kg of a potassium ricinoleate aqueous solution, 0.5kg of a hollow glass bead dispersion, 0.5kg of zinc oxide and 0.15kg of a gelling agent; curing the mixed latex in water bath at 30 ℃ for 12 hours, foaming, hot air shaping for 5 minutes, steam box vulcanizing for 30 minutes, and finally drying.
Comparative example 2
10kg of natural rubber latex, 0.7kg of a vulcanized rubber latex, 0.3kg of an aqueous solution of potassium oleate, 0.1kg of an aqueous solution of potassium ricinoleate, 0.5kg of silica powder, 0.5kg of zinc oxide and 0.15kg of a gelling agent; curing the mixed latex in water bath at 30 ℃ for 12 hours, foaming, hot air shaping for 5 minutes, steam box vulcanizing for 30 minutes, and finally drying.
Performance testing
The latex foamed products obtained in the above examples have a thickness of 5cm, and are subjected to a performance test, wherein the tensile properties are tested according to GB/T528-1998; the Shore A hardness is tested according to GB/T531-1999; the thermo-oxidative aging performance is tested according to GB/T3512-2001, and the thermo-oxidative aging condition is 100 ℃ multiplied by 22 h.
Analysis of results
(1) The difference between examples 2 and 3 and example 1 is that the grinding speed and time of the hollow glass beads have an influence on the size of the hollow glass bead fragments, and it is found by comparison that when the grinding speed is 500r/min and the grinding time is 30min, the obtained latex foamed product has the optimal density and hardness, and when the grinding speed is increased or the grinding time is prolonged, the influence on the hardness is larger, the hardness is reduced, and the density is slightly increased. Therefore, the size of the hollow glass bead fragments is controlled within a reasonable range, so that the range of the grinding rotating speed and the grinding time is given;
(2) example 5 no potassium pyrophosphate is added, because the metal ions in the hollow glass beads can affect the stability of the latex system, so that the aging performance of the latex product can be reduced by comparing example 5 with example 1, and the defect can be avoided by adding potassium pyrophosphate;
(3) the non-crushed hollow glass beads of comparative example 1 have a lower density than example 1, but do not contribute much to the increase in indentation hardness, similar to the effect of comparative example 2 using silica powder as a conventional hardener. Therefore, the hollow glass beads are crushed and then applied to the preparation of latex foaming products, so that the hardness of the products is improved, the density of the products is reduced, the excellent effect on improving the performance of the latex foaming products is achieved, and the hollow glass beads are innovative.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. A density-reducing and hardening filler for latex foaming products is a dispersion of hollow glass microsphere fragments with a solid content of 40-50%.
2. A density-reducing and stiffening filler for latex foam products according to claim 1, wherein said dispersion comprises: 2-5 parts of potassium pyrophosphate, 1-3 parts of potassium oleate solution, 48-51 parts of water and hollow glass bead fragments by mass.
3. The method for preparing a density-reducing and hardness-increasing filler for latex foam products as claimed in any one of claims 1 to 2, wherein the filler is obtained by adding a potassium pyrophosphate solution and a potassium oleate solution into water, stirring and dissolving, adding hollow glass beads, stirring uniformly, and grinding.
4. The method for preparing the density-reducing and hardness-increasing filler for latex foam product as claimed in claim 3, wherein the density of the hollow glass beads is 30-50kg/m3。
5. The method for preparing a density-reducing and hardness-increasing filler for latex foam products as claimed in claim 3 or 4, wherein the grinding is performed in a grinding tank at a rotation speed of 500-2000r/min for 20-50 min.
6. The method of claim 5, wherein the grinding tank is a vertical sanding tank.
7. The use of a density-reducing and hardness-increasing filler for latex foam according to any one of claims 1 to 2, wherein 100 parts by mass of natural latex, 4 to 7 parts by mass of a bale-vulcanization dispersant, 2 to 5 parts by mass of an aqueous solution of potassium oleate, 0.5 to 2 parts by mass of an aqueous solution of potassium ricinoleate, 5 to 10 parts by mass of the filler, 3 to 8 parts by mass of zinc oxide and 0.5 to 2 parts by mass of a gelling agent are mixed, aged in a water bath at 28 to 40 ℃ for 6 to 12 hours, foamed, hot-air set for 5 to 20 minutes, steam-cured for 10 to 30 minutes, and finally dried.
8. The use of a density-reducing and hardness-increasing filler for latex foam according to claim 7, wherein the natural latex is high ammonia natural latex with a solid content of 60%.
9. Use of a density reducing and stiffening filler for latex foam products according to claim 7 or 8, said cure package dispersion being sulphur, accelerator M and accelerator ZDC in a mass ratio of 2:1: 1.
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| CN115651282A (en) * | 2022-12-14 | 2023-01-31 | 江苏金世缘乳胶制品股份有限公司 | High-performance tara bud natural latex product and preparation process thereof |
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Application publication date: 20210716 |