CN109627468A - A kind of metal salts of organic acids phenolic resin compound and preparation method thereof - Google Patents
A kind of metal salts of organic acids phenolic resin compound and preparation method thereof Download PDFInfo
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- CN109627468A CN109627468A CN201811600037.2A CN201811600037A CN109627468A CN 109627468 A CN109627468 A CN 109627468A CN 201811600037 A CN201811600037 A CN 201811600037A CN 109627468 A CN109627468 A CN 109627468A
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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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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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
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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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
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08J2361/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with polyhydric phenols
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Abstract
The present invention relates to a kind of metal salts of organic acids phenolic resin compounds and preparation method thereof.The structure feature of the compound is that metal ion is with centered on, and carboxylic acid ion, hydroxide ion, benzene oxygen radical ion are coordination ion, are crosslinked phenolic resin in the form of coordinate bond.The compound is combined with each other by way of physical crushing blending or chemical melt blending by 100 parts of phenolic resin and 20~100 parts of metal salts of organic acids, the complex compound formed using phenolic hydroxyl group and metal salts of organic acids, forms the cross-bond of coordination mode in phenolic resin.The structure of this coordination cross-linked key can increase the intensity and heat resistance of phenolic resin, while the structure of organic acid can also increase the interface compatibility and chemical reactivity of phenolic resin Yu other materials (such as: rubber, plastics, substrate).The metal salts of organic acids phenolic resin compound can be applied in rubber, plastics and composite material.
Description
Technical field
The present invention relates to field of compound material, specifically, being to be related to a kind of metal salts of organic acids phenolic resin compound
And preparation method thereof.
Background technique
Phenolic resin chemical modification is that applied chemistry reaction changes a kind of modified of common phenol formaldehyde resin molecular structure
Method, purpose mainly improve its brittleness, cohesiveness and heat resistance, also require to improve other physical properties sometimes.Phenolic resin
Chemical modification often passes through following approach: (1) blocking phenolic hydroxyl group.Phenolic hydroxyl group etherificate or epoxidation, the phenolic hydroxyl group of phenolic resin is set to exist
Chemical reaction is not participated in resin manufacturing processes generally.(2) other components are introduced.In novolak resin, introduce with phenols,
The low molecule or high-molecular compound that aldehydes and phenol resin active point can chemically react, generating has special construction
Phenolic resin, to realize specific modified effect.For example, alkyl phenol, anacardol, tung oil, silicon compound, boron compound is added
Deng.This kind of modifications are the mainstreams of phenolic resin chemical modification.(3) inhomogeneities of strand cross-linked state is controlled.Pass through length
The molecular weight that chain raw material and special reaction are formed after being crosslinked resin has synthesis, two methods is blended, make phenolic aldehyde in bimodal distribution
Resin is cross-linked to form non-homogeneous continuous structure.(4) etherification modified phenolic resin is made containing resol resin.Common change
Learn phenol-formaldehyde resin modified include: modified by alkyl phenol, it is Pioloform, polyvinyl acetal modification, epoxy resin modification, cyanurotriamide modified, organic
Si modification, boron modification, molybdenum P Modification, xylene formaldehyde resin are modified, tung oil-modified, linseed oil is modified, it is cashew nut oil modified,
Modified, Abietyl modified, tall oil modified, alkynyl-functional of sulfonated phenolic, maleimide based polymer etc. (quoted from: Tang Lulin,
Li Naining, Wu Peixi High Performance Phenolic Resins and its application technology [M] Chemical Industry Press, 2008.).Phenolic resin
Active site be phenolic hydroxyl group, on phenyl ring the ortho position of phenolic hydroxyl group and contraposition either thermosetting phenolic methylol.Phenol hydroxyl on phenyl ring
The ortho position of base and contraposition, can be crosslinked with HMT, HMMM class curing agent makes resin solidification, and the methylol itself of thermosetting phenolic can
Make resin solidification with further polycondensation, and utilize the report of the further crosslinking curing of phenolic hydroxyl group less, " High Performance Phenolic Resins and
Its application technology " phenolic hydroxyl group of introducing phenolic resin in book do not participate in chemical reaction, block phenol generally in resin manufacturing processes
The method of hydroxyl is to make phenolic hydroxyl group etherificate or epoxidation.
The research that high adjacent position phenolic resin is reported in the article of Zhang Wenfa, introducing in phenol-formaldehyde reaction system has ortho position
The weak acid salt catalyst of divalent metal Ca, Mg, Zn, Cd, Pb, Cu, Co, Ni of inducing action, in suitable phenol/formaldehyde mole
When in the presence of the inducer of ortho position, phenol and aldehyde react at the ortho position of phenolic hydroxyl group, are formed and replace ortho-hydrogens former with methylene
High ortho position linear phenolic resin based on son is (quoted from Zhang Wenfa, Yin Yonggang, Liu Chunling, et al. high-ortho thermoplastic phenolic aldehyde tree
The synthesis of rouge and characterization [J] Shaanxi Normal University journal (from section's version), 2015,43 (1): 51-55.).These divalent metals are only
It is used to prepare high adjacent position phenolic resin only as catalyst, catalyst charge is lower.
Mu Lin, Hu Maoming are provided in the report on SAMPE China 2010 and the 9th advanced material technical seminar
High adjacent position phenolic resin polycondensation reaction equation, reaction mechanism are that phenolic hydroxyl group-divalent metal carboxylate-formaldehyde forms one kind
Complex intermediate, the contraposition that limits formaldehyde and phenolic hydroxyl group react (quoted from a kind of high ortho position phenolic aldehyde of Mu Lin, Hu Maoming
The synthesis of resin and performance study [C] //SAMPE China 2010 and the 9th advanced material technical seminar .2010.).
There are the concept for proposing metal-modified phenolic resin, the phenolic aldehyde of phenol or low order in the doctoral thesis of Northeastern University Liu Yang
Resin is reacted with some metal acid or metal halide, the alcoholates of metal or metallo-organic compound, available resistance to
The phenol-formaldehyde resin modified of hot and fire-retardant enhancing, and the phenolic resin of molybdenum, titanium, tungsten, modified zirconia is described (quoted from Liu Yang phenolic aldehyde tree
Study on graft modification [D] the Northeastern University of rouge, 2013.).
Have in Chinese patent CN103665284 and proposes alkyl phenolic resin and a kind of compound preparation of organic zinc salt modifying agent
Methods and applications.Wherein, the dosage of modifying agent zinc salts of organic acid is that 0.5~10 is added in every 100 mass parts alkyl phenolic resin
Mass parts zinc salts of organic acid.But the softening point of alkyl phenolic resin and organic acid zinc salt composite is lower than alkyl phenolic resin,
Illustrate that the crosslinking degree of alkyl phenolic resin and organic acid zinc salt composite is inadequate, leads to that its due performance could not be embodied.
Summary of the invention
The present invention provides a kind of metal salts of organic acids phenolic resin compound and its preparation sides in order to solve problem above
Method.
An object of the present invention is to provide a kind of metal salts of organic acids phenolic resin compound, and the compound has such as
Flowering structure:
Wherein, wherein R1For hydrogen (H) or methylol (HOCH2)；
R2For hydrogen (H) or hydroxyl (OH)；
R3For H, C4~C12 alkyl of linear chain or branched chain, preferably tert-butyl, Te Xinji, nonyl, dodecyl, more preferably
Tert-butyl or Te Xinji；
R4For methylene (CH2), monosulfidic bond sulphur (S), cystine linkage (S-S) or CH2-(S)m-CH2, m be 1~4 integer；
R5The saturated or unsaturated alkyl of C1~C30, the saturated or unsaturated alicyclic ring of C6~C20 for linear chain or branched chain
The aryl of base, C6~C20；
M is the transition metal of alkaline-earth metal or+divalent, preferably Mg, Ca, Zn, Co, Mn, Fe, Pb, Ni etc.；
The integer that n is 1~50, preferably 1~30 integer, more preferable 1~20 integer.
The structure feature of this metal salts of organic acids phenolic resin compound is metal salts of organic acids and phenolic resin phenol hydroxyl
Base forms complex compound, and complex compound central ion is the metal ion with coordination ability, and the coordination ion around metal ion is
Carboxylic acid ion, hydroxide ion, benzene oxygen radical ion.The advantage of this structure be make phenolic resin by phenolic hydroxyl group and metal from
The complexing of son and be further crosslinked, the glass transition temperature that this cross-linking result is embodied directly in compound increases, and resin is soft
Change point to increase.This complex structure is formed by coordinate bond and belongs to a kind of dynamic crosslinking key, and coordinate bond can be again after disconnecting
Coordinate bond is formed, reinforced resin matrix is played the role of.In addition, the formation of this coordinate bond and the phenolic hydroxyl group of phenolic resin have
It closes, phenolic hydroxyl group does not participate in chemical reaction generally during resin manufacturing processes and resin solidification are crosslinked.
The metal salts of organic acids phenolic resin compound includes that the raw material of following components is prepared, in parts by weight:
100 parts of phenolic resin；
20~100 parts of metal salts of organic acids；It is preferred that 40~60 parts.
Wherein, the phenolic resin structure is shown below:
Wherein, R1For hydrogen or methylol；R2For hydrogen or hydroxyl；R3For hydrogen, C4~C12 alkyl of linear chain or branched chain；R4For Asia
Methyl, monosulfidic bond sulphur, cystine linkage or CH2-(S)m-CH2, m be 1~4 integer；The integer that n is 1~50.
The metal salts of organic acids structure is shown below:
R5-COO-M-OOC-R5(formula 4) or R5- COO-M-OH (formula 5),
Wherein, R5It is saturated or unsaturated for the saturated or unsaturated alkyl of C1~C30, the C6~C20 of linear chain or branched chain
The aryl of alcyl, C6~C20；M is the transition metal of alkaline-earth metal or+divalent.
The second object of the present invention is to provide the preparation method of metal salts of organic acids phenolic resin compound described in one kind.
There are two types of the preparation methods of this metal salts of organic acids phenolic resin compound, i.e., physical crushing is blended and chemistry is molten
Melt blending.
Physical crushing blending method includes being pulverized and mixed the raw material by the material quantity, obtains metal salts of organic acids phenolic aldehyde
Resin compound, the mixture is heated to molten condition in use process, and to form metal salts of organic acids phenolic resin compound
Object.
Phenolic resin is crushed with high-speed mixer, metal salts of organic acids is added, is further pulverized and mixed, obtains organic acid
Metal salt phenolic resin blend, the mixture, which is heated to molten condition, in use process can form metal salts of organic acids phenol
Urea formaldehyde compound.
Preferably, the physical crushing blending method is the following steps are included: mixed the raw material by the material quantity, in temperature
High-speed stirred is crushed at 10~30 DEG C of degree, crush 3 times or more, every minor tick 30~180 seconds is heated to melting in use process
Melt state and obtains the metal salts of organic acids phenolic resin compound.It is highly preferred that being heated to 100~150 in use process
℃。
The chemistry melt-blending process is the following steps are included: mixed the raw material by the material quantity, under nitrogen protection
Phenolic resin is heated to 100~200 DEG C, reaches molten condition, metal salts of organic acids is added, increases reaction temperature extremely
It 160~210 DEG C, is stirred to react 10~60 minutes, obtains the metal salts of organic acids phenolic resin compound.
Wherein, the temperature for melting phenolic resin is preferably 130~200 DEG C, and reaction temperature is preferably 180~200 DEG C, stirring
Reaction time is preferably 20~40 minutes.
The chemistry melt-blending process specifically may include following process: phenolic resin being added in four-hole boiling flask, and installs
Reflux unit, digital display electric mixer, constant temperature electric heating set, electric energy-saving temperature controller.Under nitrogen protection, heating phenolic resin makes it
Reach molten condition, heating temperature is higher than 50 DEG C of phenolic resin softening point.Metal salts of organic acids is added under mechanical stirring, stirring is anti-
It answers, metal salts of organic acids phenolic resin compound can be obtained.
Since the compound softening point that metal salts of organic acids and phenolic resin are formed increases, the band of subsequent applications may be given
It influences, so the present invention provides two kinds of methods for preparing metal salts of organic acids phenolic resin compound.Physical crushing blending method
The raising of resin matrix softening point will not be brought, but needing to heat makes metal salts of organic acids and phenolic resin form complex compound.
The directly available metal salts of organic acids phenolic resin compound of chemical melt blending, but the softening point of compound is higher than phenolic aldehyde
Resin.
The compound softening point of this metal salts of organic acids phenolic resin and glass transition temperature increase, it may be said that bright phenolic aldehyde
Resin in the molten state with organic acid zinc with chemically reacted, generate chemical crossbond, this chemical crossbond is organic
Sour zinc is with the complexing of phenolic resin phenolic hydroxyl group as a result, it limits the movement of phenolic resin strand.This chemical crossbond
The maximum thermal decomposition temperature for also bringing along compound increases, and the promotion of this performance can widen its application field.Meanwhile it is multiple
Closing also can be as the complex reaction of organic acid zinc and phenolic resin phenolic hydroxyl group introduces organic molecule in phenolic resin structure in object
Chain, the interface compatibility that this organic molecular species chain can increase phenolic resin and rubber, plastics, substrate even chemically react
Property.In addition, this metal salts of organic acids structure compound with phenolic resin will not influence phenolic resin and further solidify, Ke Yi
So that phenolic resin is formed double cross-linked network, and then improves intensity, toughness, the heat resistance etc. of phenolic resin.
The structure of this coordination cross-linked key of the present invention can increase the intensity and heat resistance of phenolic resin, while organic acid
Structure can also increase interface compatibility and the chemical reaction of phenolic resin and other materials (such as: rubber, plastics, substrate)
Property.The metal salts of organic acids phenolic resin compound can be applied in rubber, plastics and composite material.
It is compared with the doctoral thesis of Northeastern University Liu Yang.Molybdenum phenol-formaldehyde resin modified, titanium modified phenolic resin are described in paper
The preparation process of rouge, tungsten phenol-formaldehyde resin modified, modified zirconia phenolic resin, raw material, preparation process and the present invention have obvious poor
It is different.Technology disclosed by the invention is that metal salts of organic acids and phenolic resin are compound, i.e., metal ion be with centered on, carboxylate radical from
Son, hydroxide ion, benzene oxygen radical ion are coordination ion, are crosslinked phenolic resin in the form of coordinate bond.
It is compared with the technology of Chinese patent CN103665284, the additional amount of technology metal salts of organic acids disclosed by the invention
Greater than Chinese patent CN103665284, i.e. the dosage of Chinese patent CN103665284 modifying agent zinc salts of organic acid is every 100 matter
It measures and adds 0.5~10 mass parts zinc salts of organic acid in part alkyl phenolic resin, the present invention is that the dosage of metal salts of organic acids is every
20~100 mass parts metal salts of organic acids are added in 100 mass parts alkyl phenolic resins.After metal salts of organic acids additional amount increase
The result is that make resin glass transition temperature and softening point increase, and in Chinese patent CN103665284 the result is that tree
The softening point of rouge reduces.In addition, Chinese patent CN103665284 discloses only answering for zinc salts of organic acid and alkyl phenolic resin
It closes, and the phenolic resin range that the present invention is applicable in is wider, including thermoplastic phenolic and thermosetting phenolic.
Specific embodiment
The present invention is elaborated below in conjunction with specific embodiment.It should be understood that actual use of the invention is not limited to
In embodiment.
1, raw material and reagent
1 raw material of table and reagent
2, instrument and equipment
2 instrument and equipment of table
3, analysis and test
(1) softening point is tested: testing softening point according to ASTM D3461-14.
(2) glass transition temperature measures
It opens differential scanning calorimeter (DSC), runs software, with nitrogen with constant flow rate 50mL/min purification system, when
Between not be shorter than clarification time 20min.The sample for weighing a certain amount of (usually 5-15mg is accurate to 0.1mg) is put into crucible.It allows
Heating furnace body reaches initial temperature, and sample crucible and blank crucible are put on the sensor in furnace body, steady to furnace body temperature
After start to measure.Furnace temperature is risen to 200 DEG C by 20 DEG C with the rate of 10 DEG C/min using DSC temperature programmed control, 200 DEG C of constant temperature are kept
1min, then furnace temperature is cooled to 0 DEG C by 200 DEG C with the rate of 10 DEG C/min, 0 DEG C of constant temperature keeps 1min, then with 10 DEG C/min's
Furnace temperature is risen to 200 DEG C by 0 DEG C by rate, carries out the measurement of sample glass transition temperature.Finally, instrumentation program is cooled to starting temperature
Degree, obtains the glass transition temperature of sample according to DSC curve.
(3) thermogravimetric analysis
It opens thermogravimetric analyzer (TGA), runs software, steady balance.Weigh that a certain amount of (usually 5-15mg is accurate to
Sample 0.1mg) is put into the crucible in balance sample disc.Heating furnace body is allowed to reach initial temperature, with nitrogen with constant flow rate
50mL/min purification system, time are not shorter than clarification time 20min.Furnace temperature is risen to by 20 DEG C with the heating rate of 10 DEG C/min
600 DEG C through row sample test.Finally, instrumentation program is cooled to initial temperature, the maximum heat of sample is obtained according to thermogravimetric curve
Decomposition temperature.
4, sample preparation
Embodiment 1, physical crushing blending method prepare organic acid zinc phenolic resin compound.
200g SL2005 resin is crushed with Portable high speed Universalpulverizer (ZK-100B type), 100g stearic acid is added
Zinc is further pulverized and mixed, and obtains zinc stearate-phenolic resin blend, and resin softening point is 117.2 DEG C.
The experimental method of embodiment 2~10 is same as Example 1, changes resin types, changes metal salts of organic acids type
And dosage.
3 embodiment 2~10 of table formula
| Resin | Dosage | Metal salts of organic acids | Dosage | |
| Embodiment 2 | SL-2005 | 200g | Monomethacrylate zinc | 80g |
| Embodiment 3 | SL-1401 | 200g | Zinc acetate | 60g |
| Embodiment 4 | SL-1801 | 200g | Monomethacrylate zinc | 100g |
| Embodiment 5 | SL-1801 | 200g | Zinc stearate | 80g |
| Embodiment 6 | SL-3020 | 200g | Zinc benzoate | 160g |
| Embodiment 7 | SL-3020 | 200g | Monomethacrylate zinc | 60g |
| Embodiment 8 | SL-7015 | 200g | Zinc dimethacrylate | 100g |
| Embodiment 9 | Sulfurized phenolic resin 1 | 200g | Zinc benzoate | 140g |
| Embodiment 10 | Sulfurized phenolic resin 2 | 200g | Zinc stearate | 120g |
Embodiment 11, chemical melt-blending process prepare organic acid zinc phenolic resin compound.
Phenolic resin is added in four-hole boiling flask, and reflux unit, digital display electric mixer (JJ-1), constant temperature electric heating are installed
Cover (HDM-500), electric energy-saving temperature controller (ZNHW-II type).Under nitrogen protection, heating phenolic resin reaches molten
State, heating temperature are higher than 50 DEG C of phenolic resin softening point.Metal salts of organic acids is added under mechanical stirring, is stirred to react 30min, i.e.,
Metal salts of organic acids phenolic resin compound can be obtained.
12~20 experimental method of embodiment is identical as embodiment 11, changes resin types, changes metal salts of organic acids type
And dosage.
4 embodiment 12~20 of table formula
| Resin | Dosage | Metal salts of organic acids | Dosage | |
| Embodiment 12 | SL-2005 | 200g | Monomethacrylate zinc | 80g |
| Embodiment 13 | SL-1401 | 200g | Zinc acetate | 60g |
| Embodiment 14 | SL-1801 | 200g | Monomethacrylate zinc | 100g |
| Embodiment 15 | SL-1801 | 200g | Zinc stearate | 80g |
| Embodiment 16 | SL-3020 | 200g | Zinc benzoate | 160g |
| Embodiment 17 | SL-3020 | 200g | Monomethacrylate zinc | 60g |
| Embodiment 18 | SL-7015 | 200g | Zinc dimethacrylate | 100g |
| Embodiment 19 | Sulfurized phenolic resin 1 | 200g | Zinc benzoate | 140g |
| Embodiment 20 | Sulfurized phenolic resin 2 | 200g | Zinc stearate | 120g |
Test result 1, physical crushing are blended
Calorimetry system (FP900) tests softening point, differential scanning calorimeter (DSC1 STARe System) tests glass
Glass transition temperature, thermogravimetric and synchronous solving (TGA/DSC1 STARe System) test maximum thermal decomposition temperature.
5 Examples 1 to 10 test result of table
The zinc salts of organic acid phenolic resin compound softening point of physical crushing blending method preparation is without apparent increase, compound
It is consistent with the process window of primary resin.The glass transition temperature of compound increases 2 DEG C~7 DEG C, and maximum thermal decomposition temperature increases
10 DEG C~20 DEG C.Because test sample glass transition temperature, which needs first to be warming up to sample melted state, eliminates thermal history, then
Cooling makes sample reach crystalline state, then carries out glass transition test.The glass transition temperature raising of compound illustrates phenolic aldehyde
Resin in the molten state with organic acid zinc with chemically reacted, generate chemical crossbond, the limitation of this chemical crossbond
The movement of phenolic resin strand.Zinc salts of organic acid phenolic resin compound has occurred that organic before reaching decomposition temperature
The crosslinking of sour zinc and salt phenolic resin, as a result, increasing the maximum thermal decomposition temperature of compound.
Test result 2, chemical melt-blending process
Calorimetry system (FP900) tests softening point, differential scanning calorimeter (DSC1 STARe System) tests glass
Glass transition temperature, thermogravimetric and synchronous solving (TGA/DSC1 STARe System) test maximum thermal decomposition temperature.
6 embodiment of table, 11~20 test result
The zinc salts of organic acid phenolic resin compound softening point of chemical melt-blending process preparation increases 5 DEG C~10 DEG C, and
Glass transition temperature and maximum thermal decomposition temperature raising trend are consistent with compound prepared by physical crushing blending method.Chemistry is molten
Melting compound prepared by blending method, zinc salts of organic acid and phenolic resin have occurred that cross-linking reaction during the preparation process, therefore multiple
The softening point for closing object is higher than softened original resin point, and process window should also adjust.
The above embodiment of the present invention be only be clearly illustrate examples made by the present invention, and not be to the present invention
Embodiment restriction.For those of ordinary skill in the art, it can also make on the basis of the above description
Other various forms of variations or variation.There is no necessity and possibility to exhaust all the enbodiments.It is all of the invention
Made any modifications, equivalent replacements, and improvements etc., should be included in the protection of the claims in the present invention within spirit and principle
Within the scope of.
Claims (10)
1. a kind of metal salts of organic acids phenolic resin compound, it is characterised in that the compound has the following structure:
Wherein, R1For hydrogen or methylol；R2For hydrogen or hydroxyl；
R3For hydrogen, C4~C12 alkyl of linear chain or branched chain；
R4For methylene, monosulfidic bond sulphur, cystine linkage or CH2-(S)m-CH2, m be 1~4 integer；
R5For linear chain or branched chain the saturated or unsaturated alkyl of C1~C30, the saturated or unsaturated alcyl of C6~C20, C6~
The aryl of C20；
M is the transition metal of alkaline-earth metal or+divalent；The integer that n is 1~50.
2. metal salts of organic acids phenolic resin compound according to claim 1, it is characterised in that:
R3For tert-butyl, Te Xinji, nonyl, dodecyl；M is one of Mg, Ca, Zn, Co, Mn, Fe, Pb, Ni；N be 1~
30 integer.
3. metal salts of organic acids phenolic resin compound according to claim 1, it is characterised in that the compound is by wrapping
Raw material containing following components is prepared, in parts by weight:
100 parts of phenolic resin；
20~100 parts of metal salts of organic acids.
4. metal salts of organic acids phenolic resin compound according to claim 3, it is characterised in that the compound is by wrapping
Raw material containing following components is prepared, in parts by weight:
100 parts of phenolic resin；
40~60 parts of metal salts of organic acids.
5. metal salts of organic acids phenolic resin compound according to claim 3 or 4, it is characterised in that:
The phenolic resin structure is shown below:
Wherein, R1For hydrogen or methylol；R2For hydrogen or hydroxyl；
R3For hydrogen, C4~C12 alkyl of linear chain or branched chain；
The integer that R4 is methylene, monosulfidic bond sulphur, cystine linkage or CH2- (S) m-CH2, m are 1~4；
The integer that n is 1~50；
The metal salts of organic acids structure is shown below:
Wherein, R5The saturated or unsaturated alkyl of C1~C30, the saturated or unsaturated alicyclic ring of C6~C20 for linear chain or branched chain
The aryl of base, C6~C20；M is the transition metal of alkaline-earth metal or+divalent.
6. a kind of preparation method of described in any item metal salts of organic acids phenolic resin compounds according to claim 1~5,
It is characterized by:
The preparation method includes physical crushing blending method or chemical melt-blending process.
7. the preparation method of metal salts of organic acids phenolic resin compound according to claim 6, it is characterised in that described
Physical crushing blending method the following steps are included:
The raw material is pulverized and mixed by the material quantity, obtains metal salts of organic acids phenolic resin blend, in use process
The mixture is heated to molten condition and forms metal salts of organic acids phenolic resin compound.
8. the preparation method of metal salts of organic acids phenolic resin compound according to claim 7, it is characterised in that described
Physical crushing blending method the following steps are included:
The raw material is mixed by the material quantity, high-speed stirred is crushed at 10~30 DEG C of temperature, crush 3 times or more,
Every minor tick 30~180 seconds, molten condition is heated in use process, and to obtain the metal salts of organic acids phenolic resin compound
Object.
9. the preparation method of metal salts of organic acids phenolic resin compound according to claim 6, it is characterised in that described
Chemical melt-blending process the following steps are included:
Phenolic resin is heated to 100~200 DEG C under nitrogen protection, reaches molten condition, metal salts of organic acids is added, is risen
High reaction temperature is stirred to react 10~60 minutes to 160~210 DEG C, obtains the metal salts of organic acids phenolic resin compound.
10. metal salts of organic acids phenolic resin compound according to claim 9, it is characterised in that:
The temperature for melting phenolic resin is 130~200 DEG C, and reaction temperature is 180~200 DEG C, and being stirred to react the time is 20~40
Minute.
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| CN111363110A (en) * | 2020-05-18 | 2020-07-03 | 营口理工学院 | Synthesis method of Co-modified high-carbon-residue-rate phenolic resin |
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| CN108864427A (en) * | 2017-05-08 | 2018-11-23 | 北京彤程创展科技有限公司 | A kind of sulfurized phenolic resin and preparation method thereof |
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| US4067698A (en) * | 1975-08-27 | 1978-01-10 | The Lubrizol Corporation | Bridged phenol metal salt-halo carboxylic acid condensate additives for fuels |
| CN1200378A (en) * | 1997-12-31 | 1998-12-02 | 刘宗来 | Graft copolymer of modified phenolic resin and metallic carboxylate |
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Cited By (1)
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| CN111363110A (en) * | 2020-05-18 | 2020-07-03 | 营口理工学院 | Synthesis method of Co-modified high-carbon-residue-rate phenolic resin |
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| CN109627468B (en) | 2021-11-30 |
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