CN111057275A - Constant-viscosity adhesive and preparation method thereof - Google Patents
Constant-viscosity adhesive and preparation method thereof Download PDFInfo
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- CN111057275A CN111057275A CN201811202298.9A CN201811202298A CN111057275A CN 111057275 A CN111057275 A CN 111057275A CN 201811202298 A CN201811202298 A CN 201811202298A CN 111057275 A CN111057275 A CN 111057275A
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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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
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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
- C08K5/16—Nitrogen-containing compounds
- C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
- C08K5/24—Derivatives of hydrazine
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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
- C08K5/16—Nitrogen-containing compounds
- C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
- C08K5/24—Derivatives of hydrazine
- C08K5/25—Carboxylic acid hydrazides
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Abstract
The invention provides a constant viscosity adhesive and a preparation method thereof, wherein the method comprises the following steps: mixing an aqueous solution or emulsion containing a compound of the general formula 1 and/or the general formula 2 with natural gum to obtain a permanent adhesive; the mass percentage of the compound of the general formula 1 and/or the general formula 2 is 5-50% of the total mass of the aqueous solution or the emulsion; the compound of the general formula 1 and/or the general formula 2 is used in an amount of 0.01-10 w/w% of the dry glue based on the weight of the dry glue of the natural glue; R1-NHNH2General formula 1H2NHNCO‑R2‑CONHNH2General formula 2.
Description
Technical Field
The invention relates to the field of rubber processing. More particularly relates to a constant viscosity adhesive and a preparation method thereof.
Background
The constant viscose glue can reduce the Mooney increase of the natural glue in the storage process, thereby reducing the energy consumption of the glue stock in the processing process. The traditional constant viscosity adhesive uses hydroxylamine substances, has carcinogenic risks, and has been proposed to reduce the use of the substances in the first three tire factories in the world. The traditional constant viscosity agent can affect the strength of the glue and is limited in use. In addition, the traditional constant viscosity agent also corrodes production equipment, so that the production process is strictly limited.
Therefore, there is a strong need in the art to provide a new environmentally friendly permanent adhesive with permanent adhesive effect, and at the same time, maintain good tensile properties.
Disclosure of Invention
The invention aims to provide a constant viscosity adhesive and a preparation method and application thereof.
In a first aspect of the present invention, there is provided a method for preparing a permanent adhesive, the method comprising the steps of: mixing an aqueous solution or emulsion containing a compound of the general formula 1 and/or the general formula 2 with natural gum to obtain a permanent adhesive;
the mass percentage of the compound of the general formula 1 and/or the general formula 2 is 5-50% of the total mass of the aqueous solution or the emulsion;
the compound of the general formula 1 and/or the general formula 2 is used in an amount of 0.01-10 w/w%, preferably 0.01-5 w/w%, more preferably 0.05-2 w/w% of the dry glue based on the weight of the dry glue of the natural glue;
R1-NHNH2general formula 1
H2NHNCO-R2-CONHNH2General formula 2
Wherein R1 is selected from the group consisting of hydrogen, -C (O) R3, substituted or unsubstituted C1-C30Straight or branched alkyl, radicals containing N, S and/or O atoms in the main chain, substituted or unsubstituted C3-C30Cycloalkyl, a substituted or unsubstituted non-aromatic heterocyclic ring containing N, S and/or O atoms in the ring, substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C containing N and/or S and/or O atoms6-C30Aromatic heterocyclic or fused heterocyclic;
wherein R2 is selected from the group consisting of a covalent bond, a substituted or unsubstituted C1-C30Straight or branched alkyl, radicals containing N, S and/or O atoms in the main chain, substituted or unsubstituted C3-C30Cycloalkyl, a substituted or unsubstituted non-aromatic heterocyclic ring containing N, S and/or O atoms in the ring, substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C containing N and/or S and/or O atoms6-C30Aromatic heterocyclic or fused heterocyclic;
r3 is selected from-NHNH2Substituted or unsubstituted C1-C30Straight or branched alkyl, substituted or unsubstituted C3-C30Cycloalkyl, a substituted or unsubstituted non-aromatic heterocyclic ring containing N, S and/or O atoms in the ring, substituted or unsubstituted C6-C30Aryl, substituted or notSubstituted C containing N and/or S and/or O atoms6-C30Aromatic heterocycles or fused heterocycles.
In another preferred embodiment, R1 is selected from substituted or unsubstituted C1-C12Straight or branched chain alkyl, or substituted or unsubstituted C containing N and/or S and/or O atoms6-C10Aromatic heterocycles or fused heterocycles.
In another preferred embodiment, R2 is substituted or unsubstituted C1-C12Straight or branched alkyl, substituted or unsubstituted C6-C10And (4) an aryl group.
In another preferred embodiment, R3 is substituted or unsubstituted C1-C12Straight or branched alkyl, substituted or unsubstituted C3-C10Cycloalkyl, substituted or unsubstituted C6-C10Aryl or substituted or unsubstituted C6-C10Aromatic heterocyclic ring.
In another preferred embodiment, the general formula 1 is hydrazine acetate, hydrazine propionate, hydralazine, isoniazid, 2-hydrazinoethanol, cyclohexanecarboxhydrazide, benzoylhydrazine, or carbohydrazide; the compound in the general formula 2 is oxalyl hydrazine, malonic acid dihydrazide, adipic acid dihydrazide, isophthaloyl dihydrazide or dodecanedicarboxylic acid dihydrazide.
In another preferred embodiment, the preparation method is to mix the water solution or emulsion containing the compound of the general formula 1 and/or the general formula 2 with the natural rubber latex, and then the mixture is coagulated and dried to obtain the permanent adhesive.
In another preferred embodiment, the preparation method comprises the steps of spraying or soaking the water-containing natural rubber particles with the water solution or emulsion containing the compound of the general formula 1 and/or the general formula 2, and drying to obtain the permanent adhesive.
In another preferred embodiment, the preparation method is to make the water solution or emulsion containing the compound of formula 1 and/or formula 2 in the trunk line process and the dried natural gum through stirring to obtain the permanent adhesive.
In a second aspect of the present invention, there is provided a permanent adhesive obtained by the production method provided by the present invention as described above, having a mooney viscosity stabilizing effect of ± 5, preferably ± 3.
In a third aspect of the invention, there is provided the use of a compound of formula 1 and/or formula 2 as a homoleptic agent in the preparation of a homoleptic agent;
R1-NHNH2general formula 1
H2NHNCO-R2-CONHNH2General formula 2
Wherein R1 is selected from the group consisting of hydrogen, -C (O) R3, substituted or unsubstituted C1-C30Straight or branched alkyl, radicals containing N, S and/or O atoms in the main chain, substituted or unsubstituted C3-C30Cycloalkyl, a substituted or unsubstituted non-aromatic heterocyclic ring containing N, S and/or O atoms in the ring, substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C containing N and/or S and/or O atoms6-C30Aromatic heterocyclic or fused heterocyclic;
wherein R2 is selected from the group consisting of a covalent bond, a substituted or unsubstituted C1-C30Straight or branched alkyl, radicals containing N, S and/or O atoms in the main chain, substituted or unsubstituted C3-C30Cycloalkyl, a substituted or unsubstituted non-aromatic heterocyclic ring containing N, S and/or O atoms in the ring, substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C containing N and/or S and/or O atoms6-C30Aromatic heterocyclic or fused heterocyclic;
r3 is selected from-NHNH2Substituted or unsubstituted C1-C30Straight or branched alkyl, substituted or unsubstituted C3-C30Cycloalkyl, a substituted or unsubstituted non-aromatic heterocyclic ring containing N, S and/or O atoms in the ring, substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C containing N and/or S and/or O atoms6-C30Aromatic heterocyclic or fused heterocyclic;
in another preferred embodiment, the general formula 1 is hydrazine acetate, hydrazine propionate, hydralazine, isoniazid, 2-hydrazinoethanol, cyclohexanecarboxhydrazide, benzoylhydrazine, or carbohydrazide; the compound in the general formula 2 is oxalyl hydrazine, malonic acid dihydrazide, adipic acid dihydrazide, isophthaloyl dihydrazide or dodecanedicarboxylic acid dihydrazide.
Therefore, the invention provides a novel environment-friendly constant-viscosity adhesive with a constant-viscosity effect, and the constant-viscosity adhesive can keep good tensile property.
Detailed Description
The inventors of the present invention have conducted extensive and intensive studies and found that a permanent adhesive prepared by using the compound of formula 1 and/or formula 2 as a permanent adhesive has more stable viscosity and can maintain good tensile strength. On the basis of this, the present invention has been completed.
R1-NHNH2General formula 1
H2NHNCO-R2-CONHNH2General formula 2
Wherein R1 is selected from the group consisting of hydrogen, -C (O) R3, substituted or unsubstituted C1-C30Straight or branched alkyl, radicals containing N, S and/or O atoms in the main chain, substituted or unsubstituted C3-C30Cycloalkyl, a substituted or unsubstituted non-aromatic heterocyclic ring containing N, S and/or O atoms in the ring, substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C containing N and/or S and/or O atoms6-C30Aromatic heterocyclic or fused heterocyclic;
wherein R2 is selected from the group consisting of a covalent bond, a substituted or unsubstituted C1-C30Straight or branched alkyl, radicals containing N, S and/or O atoms in the main chain, substituted or unsubstituted C3-C30Cycloalkyl, a substituted or unsubstituted non-aromatic heterocyclic ring containing N, S and/or O atoms in the ring, substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C containing N and/or S and/or O atoms6-C30Aromatic heterocyclic or fused heterocyclic;
r3 is selected from-NHNH2Substituted or unsubstituted C1-C30Straight or branched alkyl, substituted or unsubstituted C3-C30Cycloalkyl, a substituted or unsubstituted non-aromatic heterocyclic ring containing N, S and/or O atoms in the ring, substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C containing N and/or S and/or O atoms6-C30Aromatic heterocycles or fused heterocycles.
In one embodiment of the invention, R1 is selected from hydrogen, -C (O) R3, substituted or unsubstituted C1-C12Alkyl, substituted or unsubstituted C containing N and/or S and/or O atoms6-C10Aromatic heterocyclic or fused heterocyclic;
in another embodiment, R1 is selected from substituted or unsubstituted C1-C5A linear or branched alkyl group; the alkyl group is preferably a methyl, ethyl, propyl, butyl or pentyl group; the substituent group is preferably hydroxyl or halogen (fluorine, chlorine, bromine, iodine).
In one embodiment of the invention, R2 is a covalent bond, substituted or unsubstituted C1-C12Straight or branched alkyl, substituted or unsubstituted C6-C10An aryl group;
in another embodiment, R2 is substituted or unsubstituted C1-C12A linear or branched alkyl group; the alkyl group is preferably a methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, or C12 alkyl group; the substituent group is preferably hydroxyl or halogen (fluorine, chlorine, bromine, iodine).
In one embodiment of the invention, R3 is-NHNH2Substituted or unsubstituted C1-C12Straight or branched alkyl, substituted or unsubstituted C3-C10Cycloalkyl, substituted or unsubstituted C6-C10Aryl, substituted or unsubstituted C6-C10An aromatic heterocycle;
in another embodiment, R3 is substituted or unsubstituted C1-C5A linear or branched alkyl group; the alkyl group is preferably a methyl, ethyl, propyl, butyl or pentyl group; the substituent group is preferably hydroxyl or halogen (fluorine, chlorine, bromine, iodine);
in another preferred embodiment, R3 is substituted or unsubstituted C3-C6A cycloalkyl group.
In a preferred embodiment of the present invention, said general formula 1 is hydrazine acetate, hydrazine propionate, hydralazine, isoniazid, 2-hydrazinoethanol, cyclohexanecarboxhydrazide, benzoylhydrazine, or carbohydrazide; the compound in the general formula 2 is oxalyl hydrazine, malonic acid dihydrazide, adipic acid dihydrazide, isophthaloyl dihydrazide or dodecanedicarboxylic acid dihydrazide.
The preparation method of the constant viscose provided by the invention comprises the following steps:
firstly, preparing a compound of a general formula 1 and/or a general formula 2 into an aqueous solution with the mass percent of 5-50% as a constant viscosity agent;
and secondly, adding the constant viscosity agent into natural rubber latex, natural rubber particle glue or dried natural rubber (main line process) according to the proportion of 0.01-10% of the weight of the dry rubber, and uniformly mixing to obtain a constant viscosity rubber product.
In one embodiment of the present invention, for example but not limited to, in the production of SCR WF CV (domestic full emulsion constant viscosity) rubber, the constant viscosity agent is added to the natural latex in a proportion of 0.01% to 10% (preferably 0.01% to 5%, more preferably 0.05% to 2%) by weight of the dry rubber, and the mixture is mixed uniformly, and then the processes of coagulation, thinning, creping, washing, granulation, drying and the like are performed to obtain the final product.
In one embodiment of the present invention, for example but not limited to, in the production of SCR10CV (national standard size 10# viscose permanent glue), the solidified aqueous natural glue raw material is subjected to a crepe, washing and other processes, and the aqueous natural glue particles before entering the drying process are sprayed with permanent glue at a ratio of 0.01% to 10% (preferably 0.01% to 5%, more preferably 0.05% to 2%) of the dry glue weight on the aqueous natural glue particles, and then dried to obtain a permanent glue product.
In another embodiment of the invention, such as but not limited to the production of SCR10CV by the trunk line process, the raw gum material is taken as it is dried, and the constant viscosity agent and the natural collagen material are added into the extruder together in a proportion of 0.01% to 10% (preferably 0.05% to 5%, more preferably 0.05% to 2%) of the dry gum weight, and mixed uniformly to obtain the constant viscosity product.
The coagulation, ironing, creping, washing, granulating, drying, etc. processes may be performed using, but are not limited to, conventional methods, such as but not limited to coagulation using a coagulating agent including, but not limited to, formic acid, acetic acid; such as but not limited to a twin roll mill; such as, but not limited to, a creper for creping; such as but not limited to a washer; such as but not limited to a shear granulator; such as but not limited to drying equipment (generic term for drying cabinets, drying carts, pushers, ferries, and heating systems), including but not limited to drying at 50-100 deg.c.
In one embodiment of the present invention, in the first step, when the compounds of formula 1 and formula 2 are used in combination, the ratio of the amounts of the two is 1:10 to 10:1, preferably 1:5 to 5:1, and more preferably 1:3 to 3: 1.
The features mentioned above with reference to the invention, or the features mentioned with reference to the embodiments, can be combined arbitrarily. All the features disclosed in this specification may be combined in any combination, and each feature disclosed in this specification may be replaced by alternative features serving the same, equivalent or similar purpose. Thus, unless expressly stated otherwise, the features disclosed are merely generic examples of equivalent or similar features.
The main advantages of the invention are:
1. compared with the traditional hydroxylamine constant adhesive, the constant adhesive provided by the invention has low toxicity and no carcinogenicity.
2. The constant viscosity agent provided by the invention is alkalescent, and has less corrosion to equipment compared with the traditional constant viscosity agent (acidity).
3. The constant-viscosity adhesive obtained by the environment-friendly constant-viscosity adhesive provided by the invention has higher tensile strength than the traditional constant-viscosity adhesive.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers. All percentages, ratios, proportions, or parts are by weight unless otherwise specified. The weight volume percentage units in the present invention are well known to those skilled in the art and refer to, for example, the weight of solute in a 100 ml solution. 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. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The preferred embodiments and materials described herein are intended to be exemplary only.
Example 1
Preparing isoniazid into an aqueous solution with the mass percentage concentration of 10% for use; respectively adding the constant viscosity agent into the natural latex according to 0.5 percent of the weight of the dry latex (the amount of the aqueous solution with the concentration of 10 percent needs to be converted when in use), uniformly mixing, then adding the coagulant for coagulation, then performing the working procedures of thinning, creping, cleaning, granulating, drying at 50-80 ℃, and the like, and packaging to obtain the final product.
Example 2
Preparing hydrazine propionate into an aqueous solution with the mass percentage concentration of 10% for use; respectively adding the constant viscosity agent into the natural latex according to 0.5 percent of the weight of the dry latex (the amount of the aqueous solution with the concentration of 10 percent needs to be converted when in use), uniformly mixing, then adding the coagulant for coagulation, then performing the working procedures of thinning, creping, cleaning, granulating, drying at 50-80 ℃, and the like, and packaging to obtain the final product.
Example 3
Preparing oxalyl hydrazine into an aqueous solution with the mass percentage concentration of 10% for use; respectively adding the constant viscosity agent into the natural latex according to 0.5 percent of the weight of the dry latex (the amount of the aqueous solution with the concentration of 10 percent needs to be converted when in use), uniformly mixing, then adding the coagulant for coagulation, then performing the working procedures of thinning, creping, cleaning, granulating, drying at 50-80 ℃, and the like, and packaging to obtain the final product.
Example 4
Preparing carbohydrazide into an aqueous solution with the mass percentage concentration of 10% for use; respectively adding the constant viscosity agent into the natural latex according to 0.5 percent of the weight of the dry latex (the amount of the aqueous solution with the concentration of 10 percent needs to be converted when in use), uniformly mixing, then adding the coagulant for coagulation, then performing the working procedures of thinning, creping, cleaning, granulating, drying at 50-80 ℃, and the like, and packaging to obtain the final product.
Example 5
Preparing isoniazid into an aqueous solution with the mass percentage concentration of 10% for use; respectively adding the constant viscosity agent into the natural latex according to the weight of 2.0 percent of the dry latex (the amount of 10 percent of aqueous solution is converted when in use), uniformly mixing, then adding the coagulant for coagulation, then performing the working procedures of thinning, creping, cleaning, granulating, drying at 50-80 ℃, and the like, and packaging to obtain the final product.
Example 6
Preparing hydrazine propionate into an aqueous solution with the mass percentage concentration of 10% for use; respectively adding the constant viscosity agent into the natural latex according to the weight of 2.0 percent of the dry latex (the amount of 10 percent of aqueous solution is converted when in use), uniformly mixing, then adding the coagulant for coagulation, then performing the working procedures of thinning, creping, cleaning, granulating, drying at 50-80 ℃, and the like, and packaging to obtain the final product.
Example 7
Preparing oxalyl hydrazine into an aqueous solution with the mass percentage concentration of 10% for use; respectively adding the constant viscosity agent into the natural latex according to the weight of 2.0 percent of the dry latex (the amount of 10 percent of aqueous solution is converted when in use), uniformly mixing, then adding the coagulant for coagulation, then performing the working procedures of thinning, creping, cleaning, granulating, drying at 50-80 ℃, and the like, and packaging to obtain the final product.
Example 8
Preparing carbohydrazide into an aqueous solution with the mass percentage concentration of 10% for use; respectively adding the constant viscosity agent into the natural latex according to the weight of 2.0 percent of the dry latex (the amount of 10 percent of aqueous solution is converted when in use), uniformly mixing, then adding the coagulant for coagulation, then performing the working procedures of thinning, creping, cleaning, granulating, drying at 50-80 ℃, and the like, and packaging to obtain the final product.
Example 9
Preparing isoniazid and oxalyl hydrazine into 10% aqueous solution by mass percent for use; adding 0.5 percent of isoniazid and 0.5 percent of oxalyl hydrazine (the amount of the aqueous solution with the concentration of 10 percent needs to be converted when in use) according to the weight of the dry glue into the natural latex, uniformly mixing, then adding a coagulant for coagulation, and then carrying out the working procedures of thinning, creping, cleaning, granulating, drying at 50-80 ℃, and the like, and packaging to obtain the final product.
Example 10
Preparing isoniazid and carbohydrazide into an aqueous solution with the mass percentage concentration of 10% for use; adding 0.5 percent of isoniazid and 0.5 percent of carbohydrazide (the amount of 10 percent of aqueous solution is required to be converted when in use) according to the weight of dry glue into the natural latex, uniformly mixing, then adding a coagulant for coagulation, then performing processes of thinning, creping, cleaning, granulating, drying at 50-80 ℃, and the like, and packaging to obtain the final product.
Example 11
Preparing hydrazine propionate and oxalyl hydrazine into 10% aqueous solution by mass percentage for use; respectively adding 0.5 percent of hydrazine propionate and 0.5 percent of oxalyl hydrazine (the amount of the aqueous solution with the concentration of 10 percent needs to be converted when in use) according to the weight of the dry glue into the natural latex, uniformly mixing, then adding a coagulant for coagulation, and then performing the working procedures of thinning, crepe, cleaning, granulation, drying at 50-80 ℃, and the like, and packaging to obtain the final product.
Example 12
Preparing hydrazine propionate and carbohydrazide into 10% aqueous solution by mass percentage for use; respectively adding 0.5 percent of hydrazine propionate and 0.5 percent of carbohydrazide (the amount of aqueous solution with concentration of 10 percent is required to be converted when in use) according to the weight of dry glue into the natural latex, uniformly mixing, then adding a coagulant for coagulation, then performing the working procedures of thinning, creping, cleaning, granulating, drying at 50-80 ℃, and the like, and packaging to obtain the final product.
Example 13
Preparing isoniazid into an aqueous solution with the mass percentage concentration of 10% for use; respectively adding the constant viscosity agent into the natural latex according to 0.1 percent of the weight of the dry latex (the amount of the aqueous solution with the concentration of 10 percent needs to be converted when in use), uniformly mixing, then adding the coagulant for coagulation, then performing the working procedures of thinning, creping, cleaning, granulating, drying at 50-80 ℃, and the like, and packaging to obtain the final product.
Example 14
Preparing isoniazid into an aqueous solution with the mass percentage concentration of 10% for use; respectively adding the constant viscosity agent into the natural latex according to the weight of 5.0 percent of the dry latex (the amount of 10 percent of aqueous solution is converted when in use), uniformly mixing, then adding the coagulant for coagulation, then performing the working procedures of thinning, creping, cleaning, granulating, drying at 50-80 ℃, and the like, and packaging to obtain the final product.
COMPARATIVE EXAMPLE 1 (blank)
Adding a coagulant into natural latex for coagulation, then performing processes of thinning, creping, cleaning, granulating, drying at 50-80 ℃ and the like, and packaging to obtain a final product.
COMPARATIVE EXAMPLE 2 (REFERENCE)
Preparing hydroxylamine hydrochloride into an aqueous solution with the mass percentage concentration of 10% for use; respectively adding the constant viscosity agent into the natural latex according to 0.5 percent of the weight of the dry latex (the amount of the aqueous solution with the concentration of 10 percent needs to be converted when in use), uniformly mixing, then adding the coagulant for coagulation, then performing the working procedures of thinning, creping, cleaning, granulating, drying at 50-80 ℃, and the like, and packaging to obtain the final product.
COMPARATIVE EXAMPLE 3 (REFERENCE)
Preparing hydroxylamine hydrochloride into an aqueous solution with the mass percentage concentration of 10% for use; respectively adding the constant viscosity agent into the natural latex according to the weight of 2.0 percent of the dry latex (the amount of 10 percent of aqueous solution is converted when in use), uniformly mixing, then adding the coagulant for coagulation, then performing the working procedures of thinning, creping, cleaning, granulating, drying at 50-80 ℃, and the like, and packaging to obtain the final product.
TABLE 1 permanent adhesion effect and Properties of each permanent adhesive
The "constant viscosity effect" is expressed as the Mooney value of the natural gum after aging minus the original Mooney value of the natural gum, i.e., [ ML1+4 (after aging) -ML1+4 (original) ].
ML1+4 (original) refers to the mooney value of the as-produced natural gum.
ML1+4 (after aging) is the Mooney value of natural gum after standing for 7 days in an oven at 60 ℃ with phosphorus pentoxide as the water absorbent.
The Mooney value is measured at 100 ℃.
The result shows that when the environmental-friendly constant viscosity agent is added, the quality percentage is 0.5%, compared with the same amount of hydroxylamine hydrochloride, the environmental-friendly constant viscosity agent can also meet the requirement of constant viscosity index, but the obtained constant viscosity agent has higher tensile strength.
By adding a larger amount of the constant viscosity agent, the Mooney viscosity fluctuation of the obtained constant viscosity agent is smaller, namely the constant viscosity effect is better, and simultaneously, good tensile strength is obtained.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the scope of the invention, which is defined by the claims appended hereto, and any other technical entity or method that is encompassed by the claims as broadly defined herein, or equivalent variations thereof, is contemplated as being encompassed by the claims.
Claims (10)
1. The preparation method of the permanent viscose is characterized by comprising the following steps: mixing an aqueous solution or emulsion containing a compound of the general formula 1 and/or the general formula 2 with natural gum to obtain a permanent adhesive;
the mass percentage of the compound of the general formula 1 and/or the general formula 2 is 5-50% of the total mass of the aqueous solution or the emulsion;
the compound of the general formula 1 and/or the general formula 2 is used in an amount of 0.01-10 w/w% (preferably 0.01-5 w/w%, more preferably 0.05-2 w/w%) of the dry glue based on the weight of the dry glue of the natural glue;
R1-NHNH2general formula 1
H2NHNCO-R2-CONHNH2General formula 2
Wherein R1 is selected from the group consisting of hydrogen, -C (O) R3, substituted or unsubstituted C1-C30Straight or branched alkyl, radicals containing N, S and/or O atoms in the main chain, substituted or unsubstituted C3-C30Cycloalkyl, a substituted or unsubstituted non-aromatic heterocyclic ring containing N, S and/or O atoms in the ring, substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C containing N and/or S and/or O atoms6-C30Aromatic heterocyclic or fused heterocyclic;
wherein R2 is selected from the group consisting of a covalent bond, a substituted or unsubstituted C1-C30Straight or branched alkyl, radicals containing N, S and/or O atoms in the main chain, substituted or unsubstituted C3-C30Cycloalkyl, a substituted or unsubstituted non-aromatic heterocyclic ring containing N, S and/or O atoms in the ring, substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C containing N and/or S and/or O atoms6-C30Aromatic heterocyclic or fused heterocyclic;
r3 is selected from-NHNH2Substituted or unsubstituted C1-C30Straight or branched alkyl, substituted or unsubstituted C3-C30Cycloalkyl, a substituted or unsubstituted non-aromatic heterocyclic ring containing N, S and/or O atoms in the ring, substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C containing N and/or S and/or O atoms6-C30Aromatic heterocycles or fused heterocycles.
2. The method of claim 1, wherein R1 is selected from the group consisting of substituted and unsubstituted C1-C12Straight or branched chain alkyl, or substituted or unsubstituted C containing N and/or S and/or O atoms6-C10Aromatic heterocycles or fused heterocycles.
3. The method of claim 1, wherein R2 is substituted or unsubstituted C1-C12Straight or branched alkyl, substituted or unsubstituted C6-C10And (4) an aryl group.
4. The method of claim 1, wherein R3 is substituted or unsubstituted C1-C12Straight or branched alkyl, substituted or unsubstituted C3-C10Cycloalkyl, substituted or unsubstituted C6-C10Aryl or substitutedOr unsubstituted C6-C10Aromatic heterocyclic ring.
5. The method of claim 1, wherein the general formula 1 is hydrazine acetate, hydrazine propionate, hydralazine, isoniazid, 2-hydrazinoethanol, cyclohexanecarboxhydrazide, benzoylhydrazine, or carbohydrazide; the compound in the general formula 2 is oxalyl hydrazine, malonic acid dihydrazide, adipic acid dihydrazide, isophthaloyl dihydrazide or dodecanedicarboxylic acid dihydrazide.
6. The process according to any one of claims 1 to 5, wherein the permanent adhesive is obtained by mixing an aqueous solution or emulsion containing the compound of the general formula 1 and/or the general formula 2 with a natural rubber latex, coagulating and drying.
7. The process according to any one of claims 1 to 5, wherein the aqueous solution or emulsion containing the compound of formula 1 and/or formula 2 is sprayed or soaked with the aqueous natural gum particles and dried to obtain the permanent adhesive.
8. The process according to any one of claims 1 to 5, wherein the permanent adhesive is obtained by stirring an aqueous solution or emulsion containing the compound of formula 1 and/or formula 2 with the dried natural gum in a dry process.
9. A permanent adhesive obtainable by the process according to any one of claims 1 to 8.
10. A compound of formula 1 and/or formula 2 for use as a permanent adhesive in the preparation of a permanent adhesive;
R1-NHNH2general formula 1
H2NHNCO-R2-CONHNH2General formula 2
Wherein R1 is selected from the group consisting of hydrogen, -C (O) R3, substituted or unsubstituted C1-C30Straight or branched alkyl, radicals containing N, S and/or O atoms in the main chain, substituted or unsubstituted C3-C30Cycloalkyl, substitutedOr unsubstituted or non-aromatic heterocyclic ring containing N, S and/or O atoms in the ring, substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C containing N and/or S and/or O atoms6-C30Aromatic heterocyclic or fused heterocyclic;
wherein R2 is selected from the group consisting of a covalent bond, a substituted or unsubstituted C1-C30Straight or branched alkyl, radicals containing N, S and/or O atoms in the main chain, substituted or unsubstituted C3-C30Cycloalkyl, a substituted or unsubstituted non-aromatic heterocyclic ring containing N, S and/or O atoms in the ring, substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C containing N and/or S and/or O atoms6-C30Aromatic heterocyclic or fused heterocyclic;
r3 is selected from-NHNH2Substituted or unsubstituted C1-C30Straight or branched alkyl, substituted or unsubstituted C3-C30Cycloalkyl, a substituted or unsubstituted non-aromatic heterocyclic ring containing N, S and/or O atoms in the ring, substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C containing N and/or S and/or O atoms6-C30Aromatic heterocyclic or fused heterocyclic;
preferably, the general formula 1 is hydrazine acetate, hydrazine propionate, hydralazine, isoniazid, 2-hydrazinoethanol, cyclohexane carbohydrazide, benzoyl hydrazine, or carbohydrazide; the compound in the general formula 2 is oxalyl hydrazine, malonic acid dihydrazide, adipic acid dihydrazide, isophthaloyl dihydrazide or dodecanedicarboxylic acid dihydrazide.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111978602A (en) * | 2020-07-08 | 2020-11-24 | 贾中锋 | Preparation method of high-damping constant-Mooney-viscosity natural rubber and product prepared by same |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1095077A (en) * | 1993-03-02 | 1994-11-16 | 株式会社普利司通 | Natural rubber and production method thereof with constant viscosity |
| US5710200A (en) * | 1993-03-02 | 1998-01-20 | Bridgestone Corporation | Natural rubber treated with viscosity stabilizers and production thereof |
| JP2001354703A (en) * | 2000-06-15 | 2001-12-25 | Bridgestone Corp | Method for manufacturing natural rubber |
| CN1330083A (en) * | 2000-06-15 | 2002-01-09 | 株式会社普利司通 | Natural rubber latex and nutual rubber containing viscosity stabilizing agent and production method thereof |
| CN1554672A (en) * | 2003-12-23 | 2004-12-15 | 海南省农恳中心测试站 | Producing method of increasing and stabilizing adhesiveness of natural rubber |
| CN103627044A (en) * | 2013-12-12 | 2014-03-12 | 西双版纳中化橡胶有限公司 | Constant viscosity natural rubber and preparation method thereof |
| CN108570167A (en) * | 2018-05-02 | 2018-09-25 | 上海华君橡胶科技有限公司 | A kind of environmental protection natural rubber with constant viscosity and preparation method thereof |
-
2018
- 2018-10-16 CN CN201811202298.9A patent/CN111057275A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1095077A (en) * | 1993-03-02 | 1994-11-16 | 株式会社普利司通 | Natural rubber and production method thereof with constant viscosity |
| US5710200A (en) * | 1993-03-02 | 1998-01-20 | Bridgestone Corporation | Natural rubber treated with viscosity stabilizers and production thereof |
| JP2001354703A (en) * | 2000-06-15 | 2001-12-25 | Bridgestone Corp | Method for manufacturing natural rubber |
| CN1330083A (en) * | 2000-06-15 | 2002-01-09 | 株式会社普利司通 | Natural rubber latex and nutual rubber containing viscosity stabilizing agent and production method thereof |
| CN1554672A (en) * | 2003-12-23 | 2004-12-15 | 海南省农恳中心测试站 | Producing method of increasing and stabilizing adhesiveness of natural rubber |
| CN103627044A (en) * | 2013-12-12 | 2014-03-12 | 西双版纳中化橡胶有限公司 | Constant viscosity natural rubber and preparation method thereof |
| CN108570167A (en) * | 2018-05-02 | 2018-09-25 | 上海华君橡胶科技有限公司 | A kind of environmental protection natural rubber with constant viscosity and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111978602A (en) * | 2020-07-08 | 2020-11-24 | 贾中锋 | Preparation method of high-damping constant-Mooney-viscosity natural rubber and product prepared by same |
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