CN109354660B - Phenolic resin for automobile filter paper, preparation method of phenolic resin and automobile filter paper - Google Patents

Phenolic resin for automobile filter paper, preparation method of phenolic resin and automobile filter paper Download PDF

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CN109354660B
CN109354660B CN201811404902.6A CN201811404902A CN109354660B CN 109354660 B CN109354660 B CN 109354660B CN 201811404902 A CN201811404902 A CN 201811404902A CN 109354660 B CN109354660 B CN 109354660B
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filter paper
automobile
phenolic resin
catalyst
combination
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CN109354660A (en
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唐地源
李枝芳
高绍林
张宝印
唐晓莉
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Shandong Shengquan New Material Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28—Chemically modified polycondensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28—Chemically modified polycondensates
    • C08G8/32—Chemically modified polycondensates by organic acids or derivatives thereof, e.g. fatty oils
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/47—Condensation polymers of aldehydes or ketones
    • D21H17/48—Condensation polymers of aldehydes or ketones with phenols
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/08—Filter paper

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention provides a phenolic resin for automobile filter paper, a preparation method thereof and the automobile filter paper, wherein the phenolic resin for the automobile filter paper has a structure shown in a formula I, the phenolic resin containing an unsaturated bond carbon chain structure is selected as the resin for the automobile filter paper, so that the phenolic resin has better molecular toughness, the special process preparation can still keep better toughness after being subjected to a long-term high-temperature environment, the automobile filter paper prepared from the phenolic resin has the performances of ageing resistance and high temperature resistance, the performance keeping effect is good after long-term high-temperature operation, and the problem that the performance of the filter paper is reduced after long-term high-temperature operation in the prior art can be solved.

Description

Phenolic resin for automobile filter paper, preparation method of phenolic resin and automobile filter paper
Technical Field
The invention belongs to the technical field of filter paper in the automobile industry, and relates to phenolic resin for automobile filter paper, a preparation method of the phenolic resin and the automobile filter paper.
Background
The automobile filter paper is a generic name of air filter paper, engine oil filter paper and fuel filter paper for automobiles. The automobile filter paper is an important filtering material for manufacturing an air filter element, an engine oil filter and a fuel filter element, and is mainly used for filtering engine intake air, engine oil and fuel to remove dust and impurities, indirectly playing roles in lubricating, cooling and cleaning and prolonging the service life of an engine. The quality of the filter paper directly affects the efficiency and quality of the filter element filtration. With the progress of society and the improvement of living standard, medium and high-end automobiles are more and more popular, have high oil consumption, and the quality and performance of the filter paper are undoubtedly tested by high workload, so that the solid and durable filter paper can gradually replace most of the existing filter paper, and the market also increasingly demands high-quality high-end filter paper. More importantly, too many filter element replacement wastes resources, is not beneficial to the development requirement of the environment-friendly society, and increases the difficulty of environment-friendly treatment, so that the high-performance filter paper conforms to the social development trend.
CN 102391451A discloses a preparation method of phenolic resin for filter paper in automobile industry, comprising the following steps: firstly, carrying out polycondensation reaction on aldehyde and phenol with the molar ratio of 1.2-2.5: 1 at the pH value of 7.5-9.0; adding amine substances into the polycondensation product obtained in the step I, wherein the mass of the amine substances is 20-60% of that of phenol, and stirring at 75-80 ℃ for 0.5-2 hr; step three, vacuum distilling the product until the water content is less than 7.5 wt%; adding organic solvent for dilution, adding phosphate, mixing, and cooling. The phenolic resin synthesized by the method can be used for the industrial filter paper of the automobile, and the flame retardant property of the industrial filter paper is improved.
CN 104177574A discloses a phenolic resin, a preparation method thereof and automobile filter paper, wherein the phenolic resin is prepared by reacting a phenolic compound, an aldehyde compound and graphene; the molar ratio of the phenolic compound to the aldehyde compound is 1 (1.0-2.5); the mass ratio of the graphene to the phenolic compound is (0.01-2): 100. The automobile filter paper prepared from the phenolic resin has better conductivity and reduces the probability of automobile spontaneous combustion.
Therefore, in the art, the development of more excellent phenolic resins for automobile filter paper is of great significance for improving the automobile performance and the use safety.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a phenolic resin for automobile filter paper and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the present invention provides a phenolic resin for automotive filter paper, having a structure represented by formula I below:
Figure BDA0001877114210000021
wherein R is1、R2And R3Independently an unsaturated bond-containing group, x and y are independently an integer of 1 or more, and z is an integer of 0 or more.
The phenolic resin containing the unsaturated bond carbon chain structure is selected as the resin for the automobile filter paper, the long chain can provide better molecular toughness, the special process preparation enables the resin to still maintain better toughness after being subjected to a long-term high-temperature environment, and due to the fact that the activity of the unsaturated bond is higher, the unsaturated bond can replace other molecular bonds to be oxidized and broken, so that the structure of macromolecules is not influenced, and higher strength can be still maintained in the long-term high-temperature environment.
Preferably, the unsaturated bond-containing group has a carbon chain length of 3 or more carbon atoms, for example, a carbon chain length of 3 carbon atoms, 5 carbon atoms, 8 carbon atoms, 10 carbon atoms, 12 carbon atoms, 14 carbon atoms, 16 carbon atoms, 18 carbon atoms, 19 carbon atoms, 20 carbon atoms, 25 carbon atoms, 28 carbon atoms, 30 carbon atoms, etc., and preferably an unsaturated bond-containing group having a carbon chain length of 3 to 20 carbon atoms.
According to the invention, by improving the molecular structure of the phenolic resin and grafting a group containing an unsaturated bond on the basis of the original molecule, the long chain not only can provide better molecular toughness, but also can keep better toughness after being subjected to a long-term high-temperature environment due to special process preparation, and because the unsaturated bond has higher activity, the unsaturated bond can replace other molecular bonds to be oxidized and broken, so that the macromolecular structure of three-dimensional crosslinking is not influenced, the whole macromolecule is not damaged, the original strength is kept for a long time, and the uniformity is also good through experimental verification.
In the present invention, x and y are independently integers greater than 1, and may be, for example, independently 1, 2, 3, 4, 5, 6, 7, 8, 9, etc. z is an integer of 0 or more, and may be, for example, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or the like.
In the present invention, the number average molecular weight of the phenolic resin is in the range of 1000-1500. Such as 1000, 1100, 1200, 1250, 1300, 1350, 1400, 1450 or 1500, etc., if the molecular weight is too small, it will result in too much small molecular material, free raw material, unfavorable for later curing and customer application conditions, and too large a molecular weight will result in too much viscosity to suit the application environment and unfavorable for resin storage.
In another aspect, the present invention provides a method for preparing the phenolic resin for automobile filter paper, the method comprising the following steps:
(1) adding a first combined catalyst into a phenolic compound, adding a modifier, and reacting;
(2) and (2) adding a second catalyst into the reactant obtained in the step (1), adding an aldehyde compound, reacting, then adding a solvent, and cooling to obtain the phenolic resin for the automobile filter paper.
The phenolic resin prepared by the method can improve and enhance the anti-aging and high-temperature-resistant capabilities of the phenolic resin, so that the filter paper for the automobile also has the characteristics of anti-aging and high-temperature-resistant performances.
Preferably, the phenolic monomer in step (1) is selected from one or a combination of at least two of phenol, resorcinol, catechol, hydroquinone, o-cresol, p-cresol, m-cresol, xylenol or bisphenol a, preferably phenol.
Preferably, the first combination catalyst of step (1) is a combination of a lewis acid catalyst and an organic amine catalyst. The single catalyst cannot meet the process requirements.
Preferably, the molar ratio of the lewis acid catalyst to the organoamine catalyst is 1:1.2 to 1.6, such as 1:1.2, 1:1.21, 1:1.25, 1:1.28, 1:1.3, 1:1.35, 1:1.38, 1:1.4, 1:1.43, 1:1.45, 1:1.48, 1:1.5, 1:1.53, 1:1.55, 1:1.58, or 1: 1.6.
Preferably, the lewis acid catalyst is any one of formic acid, acetic acid, oxalic acid, phosphoric acid, sulfuric acid, sulfurous acid, hydrochloric acid, BrCl or p-toluenesulfonic acid or a combination of at least two thereof.
Preferably, the organic amine catalyst is any one or a combination of at least two of methylimidazole, dimethylimidazole, trimethylimidazole, ethylenediamine, diethylenediamine, or triethylamine.
Preferably, the first combination catalyst is a combination of a sulfonic acid and dimethylimidazole.
Preferably, the sulfonic acid is used in an amount of 0.1 to 2% (e.g., 0.1%, 0.11%, 0.12%, 0.13%, 0.14%, 0.15%, 0.16%, 0.17%, 0.18%, 0.19%, or 0.2%) of the amount of phenolic compound, and the dimethylimidazole is used in an amount of 0.1 to 2% (e.g., 0.1%, 0.11%, 0.12%, 0.13%, 0.14%, 0.15%, 0.16%, 0.17%, 0.18%, 0.19%, or 0.2%) of the amount of phenolic compound.
Preferably, the modifier in step (1) is a combination modifier of two or more of chloropropene, vinyl chloride, polyethylene, bromopropylene, bromoethylene, bromopropyne, phenylpropylene, styrene, stearic acid, polystyrene, acrylonitrile, butadiene, bismaleimide resin, nonylphenol, cashew nut oil, seed oil, tung oil, linseed oil, epoxidized soybean oil, polyethylene glycol, polyvinyl alcohol, polydiethylene glycol, lignin, nitrile rubber, styrene butadiene rubber, polyamide, polyurethane or phenyl ether.
Further preferably, the modifier is a combination of linseed oil and acrylonitrile.
Preferably, the linseed oil is used in an amount of 10 to 50% by mass of the phenolic compound (if less than 10%, the modification effect is poor, if more than 50% the resin does not react sufficiently to cause delamination), for example, 10%, 13%, 15%, 18%, 20%, 23%, 25%, 28%, 30%, 35%, 38%, 40%, 45%, 48% or 50%, and the acrylonitrile is used in an amount of 1 to 5% by mass of the phenolic compound (if less than 1%, the modification effect is poor, if more than 5% the resin is cured), for example, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5%.
Preferably, the temperature of the reaction in step (1) is 90-120 ℃, such as 90 ℃, 93 ℃, 95 ℃, 98 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃ or 120 ℃ and the like.
Preferably, the reaction in the step (1) is a constant temperature reaction under normal pressure.
Preferably, the reaction time in step (1) is 5 hours or more, for example, 5 hours, 7 hours, 9 hours, 10 hours, 12 hours, 15 hours, 18 hours, 20 hours, 22 hours, 24 hours, etc., preferably 5 to 12 hours. After such a reaction time, the content of free phenol detected in the reaction system of the step (1) was less than 2%.
Preferably, the temperature of the reaction system is reduced to 50-80 ℃ after the reaction of step (1), for example, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃.
Preferably, said second catalyst of step (2) is a lewis base catalyst.
Preferably, the lewis base catalyst is any one or a combination of at least two of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, barium hydroxide, magnesium oxide, calcium oxide, zinc acetate, ammonia water, hexamethylenetetramine or triethylamine, preferably hexamethylenetetramine, which is 1-5% by mass of the phenolic compound, such as 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5%.
Preferably, the aldehyde compound in step (2) is any one of formaldehyde, acetaldehyde, furfural or paraformaldehyde or a combination of at least two of them, preferably formaldehyde.
Preferably, the molar ratio of the aldehyde compound in step (2) to the phenolic compound in step (1) is 1:1 to 2.5, such as 1:1, 1:1.2, 1:1.5, 1:1.8, 1:1.9, 1:2, 1:2.2, 1:2.4 or 1: 2.5.
Preferably, the temperature of the reaction in step (2) is 70-90 ℃, such as 70 ℃, 73 ℃, 75 ℃, 78 ℃, 80 ℃, 83 ℃, 85 ℃, 88 ℃ or 90 ℃.
Preferably, the reaction in step (2) is terminated after the system viscosity reaches 50-200cp/25 ℃ (e.g., 50cp/25 ℃, 55cp/25 ℃, 58cp/25 ℃, 60cp/25 ℃, 65cp/25 ℃, 68cp/25 ℃, 70cp/25 ℃, 80cp/25 ℃, 90cp/25 ℃, 100cp/25 ℃, 120cp/25 ℃, 140cp/25 ℃, 160cp/25 ℃, 180cp/25 ℃ or 200cp/25 ℃ and the like).
Preferably, the system is subjected to vacuum dehydration treatment before adding the solvent in the step (2).
Preferably, the pressure of the vacuum dehydration treatment is-0.08 to-0.12 MPa, such as-0.08 MPa, -0.085MPa, -0.088MPa, -0.09MPa, -0.095MPa, -0.10MPa, -0.011MPa, -0.012, and the like.
Preferably, the vacuum dehydration is performed to a system moisture of less than 5%, such as 4.8%, 4.5%, 4.3%, 4%, 3.8%, 3.5%, 3%, 2.8%, 2.5%, 2%, 1.8%, 1.5%, 1.3%, 1%, 0.8%, 0.5%, 0.3%, etc.
Preferably, the solvent in step (2) is any one or a combination of at least two of methanol, ethanol, toluene, ethylene glycol, glycerol, furfuryl alcohol, acetone or butanone, preferably ethanol.
Preferably, the temperature reduction in step (2) is to be reduced to 30 ℃ or lower, such as 30 ℃, 28 ℃, 25 ℃, 22 ℃, 20 ℃, 15 ℃, 10 ℃ or the like.
In another aspect, the invention provides an automobile filter paper prepared from the phenolic resin for automobile filter paper as described above or prepared from the phenolic resin prepared by the preparation method as described above.
The automobile filter paper provided by the invention has the ageing resistance and high temperature resistance, has a good performance maintaining effect after long-time high-temperature operation, and can solve the problem that the performance of the filter paper is reduced after long-time high-temperature operation in the prior art.
Compared with the prior art, the invention has the following beneficial effects:
(1) the phenolic resin containing the unsaturated bond carbon chain structure is selected as the resin for the automobile filter paper, the long chain can provide better molecular toughness, the special process preparation enables the resin to still maintain better toughness after being subjected to a long-term high-temperature environment, and due to the fact that the activity of the unsaturated bond is higher, the unsaturated bond can replace other molecular bonds to be oxidized and broken, so that the structure of macromolecules is not influenced, and higher strength can be still maintained in the long-term high-temperature environment.
(2) The filter paper for the automobile prepared from the phenolic resin has ageing resistance and high temperature resistance, has good performance maintaining effect after long-time high-temperature operation, and can solve the problem that the performance of the filter paper is reduced after long-time high-temperature operation in the prior art.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
In this example, the phenolic resin for automobile filter paper was prepared by the following preparation method, which specifically includes the following steps:
putting 1000g of phenol into a reaction kettle, starting stirring, adding 10g of p-toluenesulfonic acid and 5g of dimethyl imidazole, adding 100g of linseed oil and 50g of acrylonitrile, heating to 100 ℃, reacting at constant temperature under normal pressure for about 3 hours, detecting free phenol, stopping the reaction when the content is less than 2%, and cooling to obtain an intermediate. And then heating the intermediate to 70 ℃, adding 30g of hexamethylenetetramine, adding 1000g (44%) of formaldehyde solution, keeping the temperature at 75-85 ℃ for reaction until the viscosity of the resin solution reaches 70cp/25 ℃, carrying out vacuum dehydration, keeping the pressure at-0.1 MPa until the water content of the system reaches 5%, adding 600g of ethanol after reaching the standard, and cooling to obtain the phenolic resin A.
The reaction formula and the product structure are as follows:
Figure BDA0001877114210000081
the nuclear magnetic characterization data are as follows:1H-NMR(d6-DMSO,δ)，6.82(s,Ph-H),5.72(s,-CH＝CH-)，6.27(s,-CH＝CH-),10.2(s,-NH-)
its number average molecular weight by GPC is Mn: 1078.
example 2
In this example, the phenolic resin for automobile filter paper was prepared by the following preparation method, which specifically includes the following steps:
putting 1000g of phenol into a reaction kettle, starting stirring, adding 2g of sulfuric acid and 5g of dimethyl imidazole, adding 150g of cashew nut oil and 50g of acrylonitrile, heating to 100 ℃, reacting at constant pressure and constant temperature, detecting free phenol after about 3 hours, stopping the reaction when the content is less than 2%, and cooling to obtain an intermediate. And then heating the intermediate to 70 ℃, adding 20g of triethylamine, adding 1100g (44%) of formaldehyde solution, keeping the temperature at 75-85 ℃ for reaction until the viscosity of the resin solution reaches 80cp/25 ℃, carrying out vacuum-pumping dehydration, keeping the pressure at-0.1 MPa until the water content of the system is less than 5%, adding 600g of ethanol after reaching the standard, and cooling to obtain the phenolic resin B.
The reaction formula and the product structure are as follows:
Figure BDA0001877114210000091
the nuclear magnetic characterization data are as follows:1H-NMR(d6-DMSO,δ)，6.82(s,Ph-H),5.72(s,-CH＝CH-)，6.27(s,-CH＝CH-),10.2(s,-NH-)
its number average molecular weight by GPC is Mn: 1510.
example 3
In this example, the phenolic resin for automobile filter paper was prepared by the following preparation method, which specifically includes the following steps:
putting 1000g of resorcinol into a reaction kettle, starting stirring, adding 10g of p-toluenesulfonic acid and 5g of dimethyl imidazole, adding 100g of nonylphenol and 40g of acrylonitrile, heating to 110 ℃, reacting at constant temperature under normal pressure for about 5 hours, detecting free phenol, stopping the reaction when the content is less than 2%, and cooling to obtain an intermediate. And then heating the intermediate to 70 ℃, adding 50g of 50% sodium hydroxide aqueous solution, adding 900g (44%) of formaldehyde solution, keeping the temperature at 75-85 ℃ for reaction until the viscosity of the resin solution reaches 60cp/25 ℃, carrying out vacuum dehydration, keeping the pressure at-0.1 MPa until the water content of the system is less than 5%, adding 600g of ethanol after reaching the standard, and cooling to obtain the phenolic resin C.
The reaction formula and the product structure are as follows:
Figure BDA0001877114210000101
the nuclear magnetic characterization data are as follows:1H-NMR(d6-DMSO,δ)，6.82(s,Ph-H),5.72(s,-CH＝CH-)，6.27(s,-CH＝CH-),10.2(s,-NH-)
the number average molecular weight was characterized by GPC as 1340.
Example 4
In this example, the phenolic resin for automobile filter paper was prepared by the following preparation method, which specifically includes the following steps:
putting 1000g of phenol into a reaction kettle, starting stirring, adding 10g of p-toluenesulfonic acid and 5g of dimethyl imidazole, adding 150g of stearic acid and 100g of styrene, heating to 85 ℃, reacting at constant temperature under normal pressure, detecting free phenol after about 3 hours, stopping the reaction when the content is less than 2%, and cooling to obtain an intermediate. And then heating the intermediate to 90 ℃, adding 40g of 18% ammonia water, adding 1000g (44%) of formaldehyde solution, keeping the temperature at 75-85 ℃ for reaction until the viscosity of the resin solution reaches 100cp/25 ℃, carrying out vacuum dehydration, keeping the pressure at-0.1 MPa until the system moisture is less than 5%, adding 800g of ethanol after reaching the standard, and cooling to obtain the phenolic resin D.
The reaction formula and the product structure are as follows:
Figure BDA0001877114210000111
the nuclear magnetic characterization data are as follows:1H-NMR(d6-DMSO,δ)，6.82(s,Ph-H),5.72(s,-CH＝CH-)，6.27(s,-CH＝CH-),10.2(s,-NH-),5.1(s,Ph-OH)
the number average molecular weight was Mn:1350 by GPC.
Example 5
In this example, the phenolic resin for automobile filter paper was prepared by the following preparation method, which specifically includes the following steps:
putting 1000g of mixed cresol into a reaction kettle, starting stirring, adding 15g of p-toluenesulfonic acid and 5g of trimethyl imidazole, adding 150g of epoxidized soybean oil and 50g of styrene, heating to 100 ℃, reacting at constant temperature under normal pressure, detecting free phenol after about 3 hours, stopping the reaction when the content is less than 2%, and cooling to obtain an intermediate. And then heating the intermediate to 70 ℃, adding 20g of hexamethylenetetramine, adding 1000g (44%) of formaldehyde solution, keeping the temperature of 75-85 ℃ for reaction until the viscosity of the resin solution reaches 90cp/25 ℃, carrying out vacuum dehydration, keeping the pressure at-0.1 MPa until the water content of the system is less than 5%, adding 600g of ethanol after reaching the standard, and cooling to obtain the phenolic resin E.
The reaction formula and the product structure are as follows:
Figure BDA0001877114210000131
the nuclear magnetic characterization data are as follows:1H-NMR(d6-DMSO,δ)，6.82(s,Ph-H),5.72(s,-CH＝CH-)，6.27(s,-CH＝CH-),10.2(s,-NH-),5.1(s,Ph-OH)
its number average molecular weight by GPC is Mn: 1128.
comparative example 1
Putting 1000g of phenol into a reaction kettle, starting stirring, adding 20g of triethylamine, adding 1200g (44%) of formaldehyde solution, heating to 80 ℃, keeping the temperature at normal pressure, controlling the viscosity of the resin to 75-85cp/25 ℃, carrying out vacuum extraction and dehydration until the water content is less than 5%, and adding 600g of ethanol to obtain the conventional phenolic resin for filter paper.
Comparative example 2
Putting 1000g of phenol into a reaction kettle, starting stirring, adding 10g of 18% ammonia water, adding 1200g (44%) of formaldehyde solution, heating to 80 ℃, keeping the temperature at normal pressure, controlling the viscosity of the resin to 65-75cp/25 ℃, carrying out vacuum dehydration until the water content is less than 5%, and adding 600g of ethanol to obtain the conventional filter paper phenolic resin.
Comparative example 3
Putting 1000g of bisphenol A into a reaction kettle, starting stirring, adding 15g of 50% sodium hydroxide aqueous solution, adding 1000g (44%) of formaldehyde solution, heating to 80 ℃, keeping the temperature at normal pressure, controlling the viscosity of the resin to be 100-grade and 110cp/25 ℃, carrying out vacuum-pumping dehydration until the moisture content is less than 5%, and adding 600g of ethanol to obtain the conventional phenolic resin for filter paper.
Example 6
The phenol resin A, B, C, D, E obtained in examples 1 to 5 and the three conventional phenol resins obtained in comparative examples 1 to 3 were diluted with ethanol to a solid content of 10% and impregnated with the same base paper for filter paper, and two pieces of filter paper were impregnated for each sample (samples obtained with different phenol resins are labeled as (1) and (2), respectively). Drying all the soaked filter paper, putting the filter paper into an oven for curing together, wherein the curing condition is 160 ℃/5 minutes, and taking out the filter paper for naturally cooling after curing.
(1) The prepared filter paper was measured for the amount of hanging glue and the degree of bursting, respectively, and recorded, and the results are shown in table 1.
(2) And cutting half of each piece of the prepared filter paper to be used for a high temperature resistance test in engine oil, cutting all the filter paper into filter paper sample blocks with the same size, dispersing the filter paper sample blocks in circulating flowing hot engine oil at 135 +/-1 ℃, keeping the temperature for 192 hours, and ensuring that each piece of sample paper is completely soaked and protected from light. After the predetermined time had elapsed, the filter paper blocks were removed and excess engine oil on the skin was adsorbed by dry filter paper, and after cooling to room temperature, the burst strength of all blocks was measured and recorded, and the results are shown in table 2.
TABLE 1
Figure BDA0001877114210000141
Figure BDA0001877114210000151
TABLE 2
Figure BDA0001877114210000152
Figure BDA0001877114210000161
As can be seen from the data in tables 1 and 2, the initial bursting strength of the filter paper made of the modified phenolic resin is almost the same as that of the filter paper made of the conventional phenolic aldehyde, the performance of the filter paper cannot be reduced, after a high-temperature performance test, the filter paper made of the modified phenolic resin is superior to the conventional resin in bursting strength, the bursting strength is reduced by 16-18% on average, and the bursting strength of the conventional resin is reduced by 42-45%, which shows that the filter paper made of the phenolic resin has more excellent ageing resistance and high-temperature resistance.
The applicant states that the present invention is described by the above examples, but the present invention is not limited to the above examples, that is, the present invention is not limited to the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (36)

1. The automobile filter paper is characterized by being prepared from a phenolic resin for the automobile filter paper, wherein the phenolic resin for the automobile filter paper has a structure shown in the following formula I:
Figure FDA0002962444170000011
wherein R is1、R2And R3Independently an unsaturated bond-containing group, x and y are independently integers of 1 or more, and z is an integer of 0 or more.
2. The filter paper for automobile according to claim 1, wherein the carbon chain length of the unsaturated bond-containing group is 3 or more carbon atoms.
3. The filter paper for automobiles as claimed in claim 1, wherein the group containing an unsaturated bond is a group containing a carbon-carbon double bond, a carbon-carbon triple bond or a carbonyl group.
4. The filter paper for automobile as recited in claim 1, wherein the phenolic resin has a number average molecular weight of 1000-1500.
5. The filter paper for the automobile as recited in claim 1, wherein the preparation method of the phenolic resin for the filter paper for the automobile comprises the following steps:
(1) adding a first combined catalyst into a phenolic compound, adding a modifier, and reacting;
(2) and (2) adding a second catalyst into the reactant obtained in the step (1), adding an aldehyde compound, reacting, then adding a solvent, and cooling to obtain the phenolic resin for the automobile filter paper.
6. The filter paper for automobile as claimed in claim 5, wherein the phenolic monomer of step (1) is selected from one or a combination of at least two of phenol, resorcinol, catechol, hydroquinone, o-cresol, p-cresol, m-cresol, xylenol or bisphenol A.
7. The filter paper for automobile as claimed in claim 6, wherein the phenolic monomer of step (1) is selected from phenol.
8. The filter paper for automobile as claimed in claim 5, wherein the first combination catalyst of step (1) is a combination of Lewis acid catalyst and organic amine catalyst.
9. The filter paper for automobile as recited in claim 8, wherein the molar ratio of the Lewis acid catalyst to the organic amine catalyst is 1: 1.2-1.6.
10. The filter paper for automobile as recited in claim 8, wherein the Lewis acid catalyst is any one of formic acid, acetic acid, oxalic acid, phosphoric acid, sulfuric acid, sulfurous acid, hydrochloric acid, or p-toluenesulfonic acid or a combination of at least two thereof.
11. The filter paper for automobile as claimed in claim 8, wherein the organic amine catalyst is any one or a combination of at least two of methylimidazole, dimethylimidazole, trimethylimidazole, ethylenediamine, diethylenediamine, or triethylamine.
12. The automotive filter paper of claim 5, wherein the first combination catalyst is a combination of sulfonic acid and dimethylimidazole.
13. The filter paper for automobile as claimed in claim 12, wherein the sulfonic acid is used in an amount of 0.1-2% by mass of the phenolic compound, and the dimethylimidazole is used in an amount of 0.1-2% by mass of the phenolic compound.
14. The filter paper for automobiles as claimed in claim 5, wherein the modifier in step (1) is a modifier for combination of two or more of chloropropene, vinyl chloride, polyethylene, bromopropylene, bromoethylene, bromopropyne, phenylpropylene, styrene, polystyrene, acrylonitrile, butadiene, bismaleimide resin, nonylphenol, cashew nut oil, seed oil, tung oil, linseed oil, epoxidized soybean oil, polyethylene glycol, polyvinyl alcohol, polyethylene glycol, lignin, nitrile rubber, styrene butadiene rubber, polyamide, polyurethane or phenylene ether.
15. The automotive filter paper of claim 14, wherein the modifier is a combination of linseed oil and acrylonitrile.
16. The filter paper for automobile as claimed in claim 15, wherein the linseed oil is used in an amount of 10-50% by mass based on the mass of the phenolic compound, and the acrylonitrile is used in an amount of 1-5% by mass based on the mass of the phenolic compound.
17. The filter paper for automobile as claimed in claim 5, wherein the temperature of the reaction in step (1) is 90-120 ℃.
18. The filter paper for automobile as claimed in claim 5, wherein the reaction in step (1) is a constant temperature reaction under normal pressure.
19. The filter paper for automobile as claimed in claim 5, wherein the reaction time in step (1) is 5 hours or more.
20. The filter paper for automobile as claimed in claim 19, wherein the reaction time of step (1) is 5-12 hours.
21. The filter paper for automobiles as claimed in claim 5, wherein the temperature of the reaction system is lowered to 50-80 ℃ after the reaction of step (1) is completed.
22. The filter paper for automobiles according to claim 5, wherein the second catalyst of step (2) is a Lewis base catalyst.
23. The filter paper for automobile as recited in claim 22, wherein the lewis base catalyst is any one of or a combination of at least two of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, barium hydroxide, magnesium oxide, calcium oxide, zinc acetate, ammonia water, hexamethylenetetramine, or triethylamine.
24. The filter paper for automobile as recited in claim 23, wherein the lewis base catalyst is hexamethylenetetramine.
25. The filter paper for automobile as claimed in claim 24, wherein the hexamethylenetetramine accounts for 1-5% of the mass of the phenolic compound.
26. The filter paper for automobiles according to claim 5, wherein the aldehyde compound in the step (2) is any one of formaldehyde, acetaldehyde, furfural or paraformaldehyde or a combination of at least two thereof.
27. The filter paper for automobile as claimed in claim 26, wherein the aldehyde compound in the step (2) is formaldehyde.
28. The filter paper for automobiles as claimed in claim 5, wherein the molar ratio of the aldehyde compound of step (2) to the phenol compound of step (1) is 1:1 to 2.5.
29. The filter paper for automobile as claimed in claim 5, wherein the temperature of the reaction of step (2) is 70-90 ℃.
30. The filter paper for automobile as claimed in claim 5, wherein the reaction in step (2) is terminated after the system viscosity is 50-200cp/25 ℃.
31. The filter paper for automobiles as claimed in claim 5, wherein the system is subjected to vacuum dehydration treatment before adding the solvent in the step (2).
32. The filter paper for automobile as claimed in claim 31, wherein the pressure of the vacuum dehydration treatment is-0.08 to-0.12 MPa.
33. The automotive filter paper of claim 31, wherein the vacuum dehydration treatment is performed until the system moisture is less than 5%.
34. The filter paper for automobile as claimed in claim 5, wherein the solvent in step (2) is any one or a combination of at least two of methanol, ethanol, toluene, ethylene glycol, glycerol, furfuryl alcohol, acetone or butanone.
35. The filter paper for automobile as claimed in claim 34, wherein the solvent in step (2) is ethanol.
36. The filter paper for automobiles as claimed in claim 5, wherein the temperature reduction in step (2) is to be 30 ℃ or less.
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CN114685742B (en) * 2020-12-31 2024-03-29 上海昶法新材料有限公司 Preparation method of phenolic resin
CN113605141A (en) * 2021-08-02 2021-11-05 安徽朋杰汽车配件有限公司 Automobile air filter assembly
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