CN105754058A - Preparation method of lignin and boron dual-modified phenolic resin and phenolic moulding plastic - Google Patents
Preparation method of lignin and boron dual-modified phenolic resin and phenolic moulding plastic Download PDFInfo
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- 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
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- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
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- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08L61/14—Modified phenol-aldehyde condensates
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Abstract
The invention relates to a preparation method of lignin and boron dual-modified phenolic resin and phenolic moulding plastic. The preparation method of the phenolic resin includes: adding lignin, an acidic catalyst and phenol into a reaction kettle, performing heating to boiling, and carrying out reflux reaction for 1-5h; adding an organic boron compound and aldehyde into the reaction solution, carrying out reaction at 90-110DEG C for 1-5h, and then performing dehydration to obtain the lignin and boron dual-modified phenolic resin. The preparation method of the phenolic molding plastic comprises the steps of: mixing the lignin and boron dual-modified phenolic resin with other raw materials evenly, and then carrying out plastication, tabletting, cooling and crushing to obtain the phenolic moulding plastic. The lignin and boron dual-modified phenolic resin and the phenolic moulding plastic prepared by the method provided by the invention have more excellent mechanical properties, better heat resistance and flame retardant performance, and better dimensional stability and electrical insulation properties.
Description
Technical field
The present invention relates to Polymer Synthesizing and technical field of modification, specifically a kind of lignin is dual with boron changes
The phenolic resin of property and the preparation method of phenolaldehyde moulding compound.
Background technology
Phenolic resin (PF) raw material sources enriches, cheap, and production technology is simple, has excellence
Mechanical performance, heat resistance, electrical insulating property, dimensional stability, molding processibility and anti-flammability, goods chi
Very little good stability, electrical insulation capability are excellent, be fuming few, it has also become the indispensable material of industrial department,
The related industries such as automobile, household electrical appliances, electric, iron and steel and house obtain application widely.Phenolic aldehyde
Resin is used for preparing the weight that phenolaldehyde moulding compound (phenolic resin composite) is phenolic resin as matrix resin
Want application, account for more than the 20% of total consumption.Phenolaldehyde moulding compound due to have good heat-resisting, electric insulation,
Dimensionally stable, the performance such as corrosion-resistant, be widely used.
As preparing the matrix resin of phenolaldehyde moulding compound, the performance of phenolic resin is to phenolaldehyde moulding compound and final
The performance of goods plays an important role, and the matrix resin preparing phenolaldehyde moulding compound at present mainly use phenol and
Formaldehyde is the phenolic resin that raw material prepares, and uses its moulding compound prepared to there is poor toughness, and heat resistance is not
The defects such as foot, simultaneously in some special application field, there is also mechanical property and the shortcoming of insulating properties deficiency.
Number of patent application be 201210492443.8 patent disclose and a kind of use lignin and boric acid modified phenolic aldehyde tree
The preparation method of fat, make use of lignin low cost, environmental protection and boric acid to improve the advantage of resin heat resistance, but
By inorganic boric acid and big molecular wood quality reactivity is low is affected, recognize phenolic resin molecule with chemical bond
Boron and the content of the lignin of participation reaction in chain are low, it is impossible to give full play to lignin and boron to phenolic aldehyde tree
The modified effect of fat.Number of patent application is 01131934.8,200910196295.3 and 201010506460.3
All have been reported that the method preparing heat resistant phenolic moulding compound etc. patent, but these mainly use physical blending process or
Improved the heat resistance of phenolaldehyde moulding compound by the method for rational allocation raw material ratio, therefore modified effect is also
Have much room for improvement.
Summary of the invention
The technical problem to be solved be to provide a kind of heat-resist, lignin that mechanical performance is high with
Phenolic resin that boron is dual modified and the preparation method of phenolaldehyde moulding compound.
In order to solve above-mentioned technical problem, the technical solution used in the present invention one is:
The preparation method of the phenolic resin that lignin is dual modified with boron, including:
Lignin, acidic catalyst are added in reactor with phenol, after being warming up to boiling, back flow reaction 1-5h；
Adding organoboron compound and aldehyde in reactant liquor, after reacting 1-5h at 90-110 DEG C, dehydration obtains
The phenolic resin that lignin is dual modified with boron.
In order to solve above-mentioned technical problem, the technical solution used in the present invention two is:
The preparation method of phenolaldehyde moulding compound, including:
By fine for the enhancing of phenolic resin dual modified with boron for the lignin of 15-45 weight portion, 10-40 weight portion
The coupling agent of dimension, the inorganic filler of 10-30 weight portion, the curing agent of 1-10 weight portion and 0.5-4 weight portion mixes
Close uniformly；
The material that mixes is sent in mill or extruder, through over-mastication, compressing tablet, cool down, pulverize after
Obtain phenolaldehyde moulding compound；
The described lignin phenolic resin dual modified with boron is according to the preparation side described in technique scheme one
The phenolic resin that the lignin that method prepares is dual modified with boron.
The beneficial effects of the present invention is: the lignin using the inventive method to prepare is dual modified with boron
Phenolic resin, compare existing phenolic resin, mechanicalness can be prepared under same process conditions
Can more excellent, the more preferable phenolaldehyde moulding compound of heat resistance, and improve the deficiency using single method of modifying,
Also reduce production cost simultaneously；The phenolaldehyde moulding compound using the inventive method to prepare, compares existing
Phenolaldehyde moulding compound, mechanical performance is more excellent, and heat resistance is more preferable, and has good cost advantage.
Detailed description of the invention
By describing the technology contents of the present invention in detail, being realized purpose and effect, give below in conjunction with embodiment
With explanation.
The design of most critical of the present invention is: 1, utilize phenol (one of reaction raw materials of phenolic resin) in acidity
Under the conditions of lignin carried out activation process, improve the reactivity of lignin, thus the beneficially later stage be by wood
Quality introduces in phenolic resin strand, and the lignin after activating can enter with organoboron compound and aldehyde
Row condensation reaction, improves the bond strength of lignin and phenol-formaldehyde resin modified；2, use containing more than 2
Active phenyl ring organoboron compound replace inorganic compounds of boron (such as boric acid) phenolic resin is modified,
The reactivity of organoboron compound is high, and can carry out condensation reaction with the lignin after activation and aldehyde,
Other reactive groups contained in organoboron compound can also react formation methylol with aldehyde, the most greatly
Improve greatly the molecular weight of phenol-formaldehyde resin modified, Boron contents and crosslink density.Phenolic resin after dual modified
Molecular weight is high, crosslink density is big, and flexible B-O key, branched structure and the high-load containing high bond energy
Boron and the existence of lignin, therefore heat resistance, toughness, anti-flammability and electrical insulating property are far above common phenolic aldehyde tree
Fat, can significantly improve the adhesion strength of phenolaldehyde moulding compound, friendship when preparing phenolaldehyde moulding compound as matrix resin
Connection density and heat resistance, has excellent heat resistance, anti-flammability, insulating properties compared with common phenolaldehyde moulding compound
And dimensional stability, the fragility of molding product is also improved, and has good cost advantage.
Concrete, the preparation method of the phenolic resin that lignin that the present invention provides is dual modified with boron, including:
Lignin, acidic catalyst are added in reactor with phenol, after being warming up to boiling, back flow reaction 1-5h；
Adding organoboron compound and aldehyde in reactant liquor, after reacting 1-5h at 90-110 DEG C, dehydration obtains
The phenolic resin that lignin is dual modified with boron.
Wherein, described lignin is preferably lignosulfonates, alkali lignin, enzymolysis xylogen, acidolysis wood
Quality or high-boiling alcohol lignin.Lignin is the material with certain molecular weight, and addition is too much, will make
The phenolic resin viscosity of preparation is excessive, poor processability, rationally selects the addition of lignin to be possible not only to fill
The lignin modifying function to phenolic resin is waved in distribution, it is also possible to prepare the phenolic resin of good fluidity, wooden
The consumption of element is preferably the 1%-50%, more preferably 10-30% of phenol quality.
Wherein, described organoboron compound at least contains 2 phenyl ring, preferably is selected from triphenyl borine acid esters, hexichol
Ylboronic acid-2-amino ethyl ester, L-positive valyl base diphenyl-borinic acids ester and L-cysteinyl-diphenyl-borinic acids ester
In one or more.Above organoboron compound contains the active phenyl ring of more than 2, can carry out with aldehyde
Condensation reaction, compared with inorganic compounds of boron, reactivity is greatly improved, and is connected to chemical bond in resin
Boron contents in strand can also be effectively controlled.It is anti-that described organoboron compound is also possible to have other
Answering group, these groups can also react with aldehyde, forms methylol.The use of described organoboron compound
Amount is preferably the 5%-50% of phenol quality.Organoboron compound contains as boron source, the phenolic resin offer for synthesis
Boron segment, although the consumption improving organoboron compound can improve the Boron contents in phenol-formaldehyde resin modified, but
Organoboron compound has multiple avtive spot, can form branched structure, therefore organic boron with phenol when reacting
The consumption of compound is also unsuitable too many, is so conducive to controlling the molecular weight when the later stage is with aldehyde reaction, is beneficial to
Industrialized production and the processing in later stage.
Wherein, described acidic catalyst can use well known to those skilled in the art for preparing phenolic resin
Any one or more acidic catalyst, preferably be selected from oxalic acid, acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, phosphonic acids,
One or more in benzene sulfonic acid and p-methyl benzenesulfonic acid, most preferably oxalic acid.The consumption of described acidic catalyst
It is preferably the 0.1-10% of phenol quality.The consumption of conservative control acidic catalyst, can improve the activation of lignin
Effect, and the phenolic resin that prepared mechanical performance and processing characteristics are all excellent.
Wherein, described phenol can use well known to those skilled in the art for preparing any one of phenolic resin
Plant phenol, preferably be selected from the one in phenol, cresols, bisphenol-A and Bisphenol F.Described aldehyde can use this area
Known to technical staff for preparing any one aldehyde of phenolic resin, preferably be selected from formaldehyde, acetaldehyde, butyraldehyde,
The formalin of the one in metaformaldehyde and paraformaldehyde, most preferably mass concentration 30-40%.
Wherein, the mol ratio of described phenol and aldehyde is preferably 0.5-1.5.Owing to organoboron compound and lignin are equal
Having the reactivity with aldehyde, it is therefore desirable to the addition of conservative control aldehyde, aldehyde very little, will make phenol, organic
Boron compound, lignin reaction's deficiency, the phenol-formaldehyde resin modified molecular weight prepared is little, and free phenol content is high,
Being unfavorable for preparing high-performance pnenolic aldehyde moulding compound, and the consumption of aldehyde is also unsuitable excessive, too much aldehyde will make product
Middle content of free aldehyde is high, and strand is long, excessive, and the viscosity of phenolic resin is too big, is unfavorable for processing, uses
The poor fluidity of its phenolaldehyde moulding compound made, processing characteristics is bad.
Concrete, the preparation method of the phenolaldehyde moulding compound that the present invention provides, including:
By fine for the enhancing of phenolic resin dual modified with boron for the lignin of 15-45 weight portion, 10-40 weight portion
The coupling agent of dimension, the inorganic filler of 10-30 weight portion, the curing agent of 1-10 weight portion and 0.5-4 weight portion mixes
Close uniformly；
The material that mixes is sent in mill or extruder, through over-mastication, compressing tablet, cool down, pulverize after
Obtain phenolaldehyde moulding compound；
The described lignin phenolic resin dual modified with boron is the phenol dual modified according to above-mentioned lignin and boron
The phenolic resin that the lignin that the preparation method of urea formaldehyde prepares is dual modified with boron.
Wherein, described reinforcing fiber can use well known to those skilled in the art for preparing phenolaldehyde moulding compound
Any one or a few reinforcing fiber, preferably be selected from carbon fiber, basalt fibre, polyester fiber, aluminum oxide
One or more in fiber, wood powder, paper powder, bamboo powder and glass fibre.Reinforcing fiber undertakes external force
Main body, can improve the mechanical performance of phenolaldehyde moulding compound.
Wherein, described inorganic filler can use well known to those skilled in the art for preparing phenolaldehyde moulding compound
Any one or a few inorganic filler, preferably be selected from calcium carbonate, talcum powder, mica powder, wollastonite powder, hard charcoal
One or more in black, magnesia, calcium oxide and flake asbestos.Inorganic filler can improve moulding compound mechanicalness
Energy, heat resistance and processing fluidity.
Wherein, described curing agent can use well known to those skilled in the art for preparing phenolaldehyde moulding compound
Any one or a few curing agent, preferably be selected from the one in methenamine, paraformaldehyde and p-methyl benzenesulfonic acid or
Multiple.The addition of curing agent can make resin solidify, and is connected with each other between little molecule, forms macromolecular chain, makes
Obtain composite product and form cross-linked structure, improve mechanical performance and the insulating properties of goods.
Wherein, described coupling agent can use well known to those skilled in the art for preparing phenolaldehyde moulding compound
Any one or a few coupling agent, preferably be selected from titanate coupling agent, aluminate coupling agent, silane coupler,
One or more in boric acid ester coupler and phosphate coupling agent.Coupling agent is interface modifier, can improve
Inorganic filler and the interface performance of resin, make inorganic filler reach preferably and disperse, to improving composite system
The mechanical performance of product and heat resistance etc. all have good result.
By foregoing description, the beneficial effects of the present invention is: use the inventive method to prepare
The phenolic resin that lignin is dual modified with boron, compares existing phenolic resin, under same process conditions
Can prepare that mechanical performance is more excellent, the more preferable phenolaldehyde moulding compound of heat resistance, and it is single to improve employing
The deficiency of modified method, also reduces production cost simultaneously；Use the phenolic aldehyde that the inventive method prepares
Moulding compound, compares existing phenolaldehyde moulding compound, and mechanical performance is more excellent, and heat resistance is more preferable, and has very
Good cost advantage.
Embodiment 1
1) phenol of the enzymolysis xylogen of 25 weight portions, the oxalic acid of 1 weight portion and 100 weight portions is added instead
Answer in still, after being warming up to boiling, back flow reaction 5h；
2) to step 1) reactant liquor in add diphenyl-borinic acids-2-amino ethyl ester and 80 weights of 10 weight portions
The formaldehyde of amount part, after reacting 5h at 100 DEG C, dehydration obtains the phenolic resin that lignin is dual modified with boron.
Embodiment 2
1) phenol of the calcium lignosulfonate of 15 weight portions, the oxalic acid of 0.9 weight portion and 100 weight portions is added
Enter in reactor, after being warming up to boiling, back flow reaction 3h；
2) to step 1) reactant liquor in add 30 weight portions L-positive valyl base diphenyl-borinic acids ester and
The mass concentration of 95 weight portions is the formalin of 37%, and after reacting 2h at 100 DEG C, dehydration obtains wood
The phenolic resin that quality is dual modified with boron.
Embodiment 3
1) phenol of the high-boiling alcohol lignin of 30 weight portions, the oxalic acid of 5 weight portions and 100 weight portions is added
In reactor, after being warming up to boiling, back flow reaction 5h；
2) to step 1) reactant liquor in add 10 weight portions L-cysteinyl-diphenyl-borinic acids ester and
The metaformaldehyde of 80 weight portions, after reacting 5h at 100 DEG C, it is dual modified with boron that dehydration obtains lignin
Phenolic resin.
The carbon fiber modifying phenolic resin that above-described embodiment 1-3 is prepared and unmodified common phenolic aldehyde tree
Fat contrasts, and control methods is as follows:
The lignin prepared by above-described embodiment 1-3 phenolic resin dual modified with boron is according to shown in table 1
Formula prepare phenolaldehyde moulding compound (consumption unit is weight portion), by unmodified phenolic resin according to table
Formula shown in 2 prepares phenolaldehyde moulding compound (consumption unit is weight portion).The phenol that lignin is dual modified with boron
The method that urea formaldehyde and phenolic resin prepare phenolaldehyde moulding compound is as follows:
1) weigh each raw material according to formula shown in form, each raw material is added in mixer and mixes；
2) material that mixes is sent in mill or extruder, through over-mastication, compressing tablet, cool down, pulverize
After obtain phenolaldehyde moulding compound.
The formula of table 1 phenolaldehyde moulding compound
The formula of table 2 phenolaldehyde moulding compound
The performance test data of each embodiment and comparative example is as shown in table 3 below.
Table 3 performance data contrasts
Knowable to shown in above-mentioned table 3, under same raw material, proportion and technology condition, use the present invention's
The phenolaldehyde moulding compound obtained by phenolic resin that lignin is dual modified with boron, compares employing unmodified commonly
Phenolaldehyde moulding compound obtained by phenolic resin, has the most excellent heat resistance and mechanical performance, and size is steady
Qualitative preferable with electrical insulation capability.
The foregoing is only embodiments of the invention, not thereby limit the scope of the claims of the present invention, every profit
The equivalents made by description of the invention content, or directly or indirectly it is used in relevant technical field,
The most in like manner it is included in the scope of patent protection of the present invention.
Claims (10)
1. the preparation method of the phenolic resin that lignin is dual modified with boron, it is characterised in that including:
Lignin, acidic catalyst are added in reactor with phenol, after being warming up to boiling, back flow reaction 1-5h；
Adding organoboron compound and aldehyde in reactant liquor, after reacting 1-5h at 90-110 DEG C, dehydration obtains
The phenolic resin that lignin is dual modified with boron.
The preparation method of the phenolic resin that lignin the most according to claim 1 is dual modified with boron, its
It is characterised by: described lignin is lignosulfonates, alkali lignin, enzymolysis xylogen, acidolysis lignin
Or high-boiling alcohol lignin, the consumption of described lignin is the 1%-50% of phenol quality.
The preparation method of the phenolic resin that lignin the most according to claim 1 is dual modified with boron, its
It is characterised by: described organoboron compound is selected from triphenyl borine acid esters, diphenyl-borinic acids-2-amino ethyl ester, L-
One or more in positive valyl base diphenyl-borinic acids ester and L-cysteinyl-diphenyl-borinic acids ester, described
The consumption of organoboron compound is the 5%-50% of phenol quality.
The preparation method of the phenolic resin that lignin the most according to claim 1 is dual modified with boron, its
It is characterised by: described acidic catalyst is selected from oxalic acid, acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, phosphonic acids, benzene sulphur
One or more in acid and p-methyl benzenesulfonic acid, the consumption of described acidic catalyst is the 0.1-10% of phenol quality.
The preparation method of the phenolic resin that lignin the most according to claim 1 is dual modified with boron, its
Being characterised by: described phenol one in phenol, cresols, bisphenol-A and Bisphenol F, described aldehyde is selected from first
One in aldehyde, acetaldehyde, butyraldehyde, metaformaldehyde and paraformaldehyde, the mol ratio of described phenol and aldehyde is 0.5-1.5.
6. the preparation method of phenolaldehyde moulding compound, it is characterised in that including:
By fine for the enhancing of phenolic resin dual modified with boron for the lignin of 15-45 weight portion, 10-40 weight portion
The coupling agent of dimension, the inorganic filler of 10-30 weight portion, the curing agent of 1-10 weight portion and 0.5-4 weight portion mixes
Close uniformly；
The material that mixes is sent in mill or extruder, through over-mastication, compressing tablet, cool down, pulverize after
Obtain phenolaldehyde moulding compound；
The described lignin phenolic resin dual modified with boron is according to described in claim 1-5 any one
The phenolic resin that the lignin that preparation method prepares is dual modified with boron.
The preparation method of phenolaldehyde moulding compound the most according to claim 6, it is characterised in that: described enhancing
Fiber selected from carbon fiber, basalt fibre, polyester fiber, alumina fibre, wood powder, paper powder, bamboo powder and
One or more in glass fibre.
The preparation method of phenolaldehyde moulding compound the most according to claim 6, it is characterised in that: described inorganic
Filler is selected from calcium carbonate, talcum powder, mica powder, wollastonite powder, white carbon, magnesia, calcium oxide and asbestos
One or more in powder.
The preparation method of phenolaldehyde moulding compound the most according to claim 6, it is characterised in that: described solidification
One or more in methenamine, paraformaldehyde and p-methyl benzenesulfonic acid of agent.
The preparation method of phenolaldehyde moulding compound the most according to claim 6, it is characterised in that: described idol
Connection agent is selected from titanate coupling agent, aluminate coupling agent, silane coupler, boric acid ester coupler and phosphate
One or more in coupling agent.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106589799A (en) * | 2016-12-16 | 2017-04-26 | 沙县宏盛塑料有限公司 | Lignin modified phenolic resin based composite material and preparation method thereof |
| CN106633622A (en) * | 2016-09-21 | 2017-05-10 | 沈阳化工大学 | Phenolic resin containing zeatin perssad and preparation method thereof |
| CN106750062A (en) * | 2016-12-16 | 2017-05-31 | 沙县宏盛塑料有限公司 | A kind of phenolic resin of modified by cardanol and the preparation method of phenolaldehyde moulding compound |
| CN110144046A (en) * | 2019-05-28 | 2019-08-20 | 沙县宏盛塑料有限公司 | A kind of preparation method of boracic phenolic resin microspheres and carbosphere |
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| CN106633622A (en) * | 2016-09-21 | 2017-05-10 | 沈阳化工大学 | Phenolic resin containing zeatin perssad and preparation method thereof |
| CN106633622B (en) * | 2016-09-21 | 2018-10-12 | 沈阳化工大学 | A kind of phenolic resin and preparation method thereof containing zeatin group |
| CN106589799A (en) * | 2016-12-16 | 2017-04-26 | 沙县宏盛塑料有限公司 | Lignin modified phenolic resin based composite material and preparation method thereof |
| CN106750062A (en) * | 2016-12-16 | 2017-05-31 | 沙县宏盛塑料有限公司 | A kind of phenolic resin of modified by cardanol and the preparation method of phenolaldehyde moulding compound |
| CN110144046A (en) * | 2019-05-28 | 2019-08-20 | 沙县宏盛塑料有限公司 | A kind of preparation method of boracic phenolic resin microspheres and carbosphere |
| CN110144046B (en) * | 2019-05-28 | 2021-05-28 | 沙县宏盛塑料有限公司 | Boron-containing phenolic resin microspheres and preparation method of carbon microspheres |
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