CN107892752A - A kind of multi-functional lignin arylamine macromolecular antioxidant and its preparation method and application - Google Patents
A kind of multi-functional lignin arylamine macromolecular antioxidant and its preparation method and application Download PDFInfo
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Abstract
Application the invention provides a kind of novel and multifunctional property lignin arylamine macromolecular antioxidant and preparation method thereof and in the polymer.Arylamine is incorporated into lignin phenol ortho position by the present invention by Mannich reaction, the phenolic functions of lignin is changed into the more preferable hindered phenol structure of antioxidant effect, is improved its antioxidant capacity；The introducing of arylamine will further enhance antioxidant effect simultaneously, play a part of cooperateing with antioxygen.Compared with common antioxidant polymer, the lignin arylamine macromolecular antioxidant for preparing of the present invention has that nontoxic, molecular weight is high, not easy to migrate, addition is low, technique is simple, mild condition, is easy to many advantages, such as industrialized production.
Description
Technical field
The present invention relates to antioxidant polymer technical field, and in particular to a kind of multi-functional lignin arylamine macromolecular
Antioxidant and preparation method thereof and the application in processing of high molecular material.
Background technology
It is vulnerable to the influence of the external environments such as heat, oxygen, light during polymer production processing, storage, use, divides
Subchain fracture, degraded or the phenomenon for being crosslinked and causing polymeric material performance to reduce, referred to as aging.Add in the polymer
Antioxidant (also known as age resistor) can suppress the aging phenomena such as the hot oxygen of polymer, ultraviolet, ozone, improve the materials'use life-span.
At present, conventional antioxidant mainly has arylamine class, Hinered phenols etc., and its main function mechanism is to catch polymer
Free radical caused by molecular chain degradation, restrain strand and be further broken.Conventional arylamine kind antioxidant is diphenylamines or right
The derivative of phenylenediamine, it is mainly used in the rubber of dark color, it is all to have that cost is low, antioxygen efficiency high, combination property are good etc.
More advantages.There is also the shortcomings of poisonous, contaminative, property easy to change, should not be used in light environmental protection polymerization for arylamine kind antioxidant simultaneously
Tetramune.The potential toxicity of arylamine kind antioxidant is that its is easy to migrate to product surface or dissolution in polymer body and by people
Body contacts.For disadvantage mentioned above, low volatilization, stability are good, resistance to migration, resistance to dissolution, nontoxic arylamine kind antioxidant are that such resists
The R＆D direction of oxygen agent.
Hinered phenols antioxidant due to its hypotoxicity, it is not easy to change, pollution-free the advantages that, in terms of polymers against oxidative
Quickly grow.But the shortcomings such as Hinered phenols antioxidant is present, and molecular weight is low, heat endurance is poor, easy to migrate, antioxidant effect is low, lead
Its application is caused to be restricted.In order to overcome the disadvantages mentioned above of Hinered phenols antioxidant, a kind of resolving ideas is that synthesizing new divides greatly
Sub- Hinered phenols antioxidant.The A of Publication No. CN 104292141 Chinese patent discloses a kind of Sulfide-containing Hindered and carbamic acid
The synthetic method of the macromolecular hindered phenol antioxygen of ester group and its application；The A of Publication No. CN 105061639 China is specially
Profit discloses a kind of macromolecular antioxidant for containing seven hindered phenol groups, to overcome conventional macromolecular hindered phenol antioxygen effective
The shortcomings that composition is low.The above novel macromolecule hindered phenol antioxygen synthetic method is complicated, and cost is higher, causes its application
It is restricted.
Lignin is a kind of natural aromatic polymer, is widely present in higher plant.Industrial lignin main source
In modern pulping back liquor and wood-based composites industry, its yield is huge, but is often directly discharged as trade waste
To rivers,lakes and seas or burn.Because lignin macromolecular contains a large amount of phenolic groups for being similar to hindered phenol structure, thus it is wooden
Element is also believed to a kind of inexpensive natural macromolecular Hinered phenols antioxidant.Meanwhile lignin molecule has good purple
Outer absorbent properties, polymeric U aging can be prevented.There is more text on application of the lignin as antioxidant in the polymer
Offer report, but due to and not all lignin macromolecular phenolic groups be hindered phenol structure, and many phenolic groups are embedded in
Intramolecule so that lignin antioxygen is less efficient.Good antioxygen can be played when largely filling lignin in the polymer
Effect but polymer performance can be caused to reduce.Thus, it is that lignin should as high-efficiency anti-oxidant to improve lignin antioxygenic activity
Premise.
The A of Publication No. CN 106589403 Chinese patent discloses one kind by laccase lignin degrading so as to improve
The method of lignin antioxidation activity, but lignin molecule phenolic groups are not substantially changed into hindered phenol by this method
Structure, and merely by lignin molecule amount is reduced, more phenolic groups are exposed to realize the high antioxygenic activity of lignin,
And in terms of its application is not directed to antioxidant polymer.On the other hand, on preparing the pertinent literature and patent of lignin amine
Report more, but be to be incorporated into lignin molecule to use as cationic emulsifier using aliphatic amine mostly, be not directed to arylamine
With the reaction of lignin, and antioxygen property (such as Chinese patent CN 104693450 A, CN of lignin arylamine are not directed to
104592530 A、CN 106750364 A)。
It is used as the disadvantage mentioned above present in antioxidant for existing antioxidant polymer and lignin, the present invention provides one
Multi-functional lignin arylamine macromolecular antioxidant of kind and its preparation method and application.
The content of the invention
It is an object of the invention to overcome existing lignin as antioxygen efficiency existing for polymers against oxidative agent is low, shadow
The deficiencies of ringing polymer performance, there is provided a kind of inexpensive, less toxic, efficient multi-functional lignin arylamine macromolecular antioxidant,
The structure of the novel antioxidant is as follows：
Wherein, R1Selected from hydrogen or methoxyl group, R2It is selected from In one kind.
Another object of the present invention is to provide a kind of preparation side of multi-functional lignin arylamine macromolecular antioxidant
Method, comprise the following steps：(a) with water as solvent, lignin, arylamine are mixed in proportion, regulation pH value of solution to alkalescence；
(b) under protective atmosphere, formaldehyde, temperature reaction are added into mixed solution；(c) mixed solution pH is adjusted after the completion of reacting to acid
Property, continue to heat up, filtered after luming, washing is dried to obtain lignin arylamine macromolecular antioxidant.
In such scheme step (a), mass ratio when lignin, arylamine, water mix is 100：10~150：400~
900。
In such scheme step (b), the addition of formaldehyde is (6-12) % of lignin quality.
In such scheme, sodium hydrate regulator solution pH to 10.5-12 is used before reacting, it is molten with dilute sulfuric acid regulation after reaction
Liquid pH to 2-3.
In such scheme, 45-80 DEG C of reaction temperature, hour in reaction time 1-3, react and mixed solution pH is adjusted to acid
Property, 80-90 DEG C is warming up to, is filtered after caking and multiple (3-5 times) with hot wash, to remove unreacted small molecule and nothing
Machine salt；(3 times) then are washed with absolute ethyl alcohol, to remove unreacted arylamine molecule；It is true that product is finally placed in 60 DEG C of environment
Sky is dried 24 hours and produced.
In such scheme, the lignin be alkali lignin, sulfate-reducing conditions, enzymolysis xylogen, acetic acid lignin,
High-boiling alcohol lignin, acetone lignin, ammonia lignin, phenol lignin, ionic liquid lignin, explosion lignin, overcritical extraction
Take any one or more mixture formed in lignin and organosolv lignin.
In such scheme, the arylamine is any one in aniline, p-phenylenediamine, diphenylamines, 4-aminodiphenylamine
Or the mixture of a variety of formation.
The present invention also provides a kind of application of lignin arylamine macromolecular antioxidant in the polymer, according to 0.1-3:100
Mass ratio by obtained lignin arylamine macromolecular antioxidant be added in polymer be well mixed, the polymer includes
Natural rubber, butadiene-styrene rubber, nitrile rubber, butadiene rubber, polypropylene, antioxidant addition manner include directly be kneaded with rubber,
It is blended with rubber latex blending, with polypropylene fusion.
In such scheme, method of the lignin arylamine macromolecular antioxidant directly with compounding rubber is specially：Rubber is thin logical
Afterwards, stearic acid, zinc oxide, accelerant CZ, altax and lignin arylamine macromolecular antioxidant are added and is kneaded uniformly,
Then carbon black and sulphur are added, slice after being kneaded uniformly, the elastomeric compound containing lignin arylamine macromolecular antioxidant is obtained, stops
Put after cure；
The method that lignin arylamine macromolecular antioxidant is blended with rubber latex is specially：By lignin arylamine macromolecular
Antioxidant is added in 0.1mol/L sodium hydroxide solution, is configured to the antioxidant solution of 10% solid content, and antioxidant is molten
Liquid is added in the rubber latex of solid content 60%, is uniformly mixed, and is then demulsified with 1mol/L watery hydrochloric acid and is used deionization
Water washing, the rubber raw rubber of the macromolecular antioxidant of arylamine containing lignin is dried to obtain, is finally kneaded and vulcanizes according to preceding method；
Lignin arylamine macromolecular antioxidant is specially with polypropene blended method：It is at room temperature that lignin arylamine is big
Molecule antioxidant and polypropylene mechanical mixture are uniform, then the extruding pelletization in double screw extruder, extrusion temperature 180-
200 DEG C, finally by pellet injection molding, injection temperature is 190 DEG C.
A kind of multi-functional lignin arylamine macromolecular antioxidant provided by the invention, combine lignin it is nontoxic and into
This low and advantage that arylamine antioxidant effect is good, while arylamine small molecule is incorporated into phenol ortho, by lignin it is non-by
The phenolic groups of resistance phenol structure are changed into hindered phenol structure, reach low cost, resistance to migration, resistant to extraction, asepsis environment-protecting and efficiently resist
Hot oxygen and the multiple effect with UV resistance aging.The multi-functional lignin arylamine macromolecular antioxidant can be in rubber and depth
Used in color rubber, there is the advantages of addition is low, antioxygenic activity is high.The multi-functional lignin arylamine macromolecular resists
Oxygen agent can not only be blended directly with compounding rubber or with plastic molten melt, and because it has the characteristics of being dissolved in aqueous slkali,
As rubber antioxygen in use, can disperse directly in rubber latex, it is coprecipitated by being demulsified so that the macromolecular antioxygen
Agent dispersiveness in rubber improves, and antioxidant effect is notable；Again or, after first being mixed in aqueous with hydrophilic filler
Dry and filled polymer, improve filler and polymer compatibility and it is dispersed while, improve its in the polymer scattered
Property, to reach more preferable antioxidant effect.
Compared with prior art, the invention has the advantages that：Used raw material is natural phenolic polymer,
It is nontoxic, renewable, it is cheap and easy to get, and itself there is certain antioxygenic activity；Arylamine is incorporated into lignin by Mannich reaction
Phenol ortho, the phenolic functions of lignin is changed into the more preferable hindered phenol structure of antioxidant effect, improve its antioxygen energy
Power, while the introducing of arylamine will further enhance antioxidant effect, play a part of cooperateing with antioxygen；With common polymer antioxygen
Agent is compared, and the lignin arylamine macromolecular antioxidant prepared by the present invention is nontoxic, and molecular weight is high, and not easy to migrate, addition is low,
Technique is simple, mild condition, is easy to industrialized production.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of each material in the embodiment of the present invention 1, and (a) is lignin arylamine, (b) is N- phenyl pair
Phenylenediamine, (c) are lignin.
Embodiment
To make those of ordinary skill in the art fully understand technical scheme and beneficial effect, below in conjunction with tool
Body embodiment is further described.
Involved reaction is as follows in preparation process of the present invention：
Wherein R1Selected from-H or-OCH3In one kind, R2It is selected from In one kind.
Embodiment 1
(1) alkali lignin and 4-aminodiphenylamine mixed solution are prepared：By alkali lignin, 4-aminodiphenylamine, water
In mass ratio 100：44.2：800 are added in three-necked flask, and it is 12 to add sodium hydrate regulator solution pH value, at 70 DEG C
Heating stirring 1 hour, makes alkali lignin fully be dissolved with 4-aminodiphenylamine, is well mixed.
(2) react：Under nitrogen protection, formaldehyde (addition 6g first is slowly added dropwise into mixed solution obtained by step (1)
Aldehyde/100g lignin), and the heating stirring under the conditions of 70 DEG C, react 3 hours.
(3) purification of products：With 5% sulfuric acid solution regulating step (2) resulting solution pH value to 2.5, it is warming up to 90 DEG C and protects
Temperature, filter after luming, first with hot water wash 5 times, to remove unreacted small molecule and inorganic salts, then washed with absolute ethyl alcohol
Wash 3 times, to remove unreacted arylamine molecule.Finally, refined product is placed in 60 DEG C of vacuum drying chambers dry it is 24 small
When, that is, obtain lignin arylamine macromolecular antioxidant.
Lignin arylamine macromolecular antioxidant structural formula is as follows made from the present embodiment：
The infrared spectrogram of raw material 4-aminodiphenylamine, lignin and product is as shown in Figure 1.Fig. 1 illustrates N- phenyl pair
Phenylenediamine is successfully introduced into lignin molecule phenolic groups ortho position.
(4) application of the lignin arylamine macromolecular antioxidant in natural rubber：By 100 parts of natural rubbers in mill
After going up thin lead to 8 times, it is above-mentioned to sequentially add 2 parts of stearic acid, 5 parts of zinc oxide, 1.5 parts of accelerant CZs, 0.5 part of altax and 1 part
The lignin arylamine macromolecular antioxidant of synthesis, 30 parts of N330 carbon blacks and 1.5 parts of sulphur are then added, gone out after being kneaded uniformly
Piece obtains elastomeric compound.Elastomeric compound parks the tabletting vulcanization on 25 tons of hydraulic flat vulcanizers after 24h, and curing temperature is 143 DEG C,
Cure time is 387s, and the sample after vulcanization carries out accelerating thermo-oxidative ageing test and resistant to extraction to survey after room temperature parks 24h
Examination.
Embodiment 2
Other steps of the present embodiment are same as Example 1, and difference is the lignin arylamine macromolecular antioxygen synthesized
Application of the agent in natural rubber is using the mode being blended with Heveatex：By the lignin arylamine macromolecular of 1 part of synthesis
Antioxidant is added to the antioxidant solution that 10% solid content is configured in a certain amount of 0.1mol/L sodium hydroxide solution, will be upper
State antioxidant solution and be added in the natural rubber latex of 167 parts of solid contents 60% (100 parts of rubbers), be mixed and stirred for uniformly,
Then it is demulsified and is washed with deionized with 1mol/L watery hydrochloric acid, is finally dried to obtain the macromolecular antioxidant of arylamine containing lignin
Natural rubber rubber.The step of preparing elastomeric compound and vulcanizate afterwards and formula are same as Example 1, corresponding vulcanization
Time is 413s.
Embodiment 3
Other steps of the present embodiment are same as Example 1, and difference is：Alkali lignin, N- phenyl in step (1)
P-phenylenediamine, water quality ratio are 100：66.3：900, formaldehyde dosage is 9g/100g lignin in step (2), when accordingly vulcanizing
Between be 372s.
Embodiment 4
Other steps of the present embodiment are same as Example 1, and difference is：4-aminodiphenylamine changes in step (1)
Into p-phenylenediamine, alkali lignin, p-phenylenediamine, water quality ratio are 100：54：500, formaldehyde dosage is 12g/ in step (2)
100g lignin, step (4) prepare the natural of the macromolecular antioxidant of arylamine containing lignin by the way of being blended with Heveatex
Rubber raw rubber, elastomeric compound and vulcanizate, corresponding cure time are 366s.
Lignin arylamine macromolecular antioxidant molecular structure is as follows made from the present embodiment：
Embodiment 5
Other steps of the present embodiment are same as Example 1, and difference is：The lignin arylamine macromolecular of synthesis resists
Oxygen agent is applied to polypropylene, and specific method is：By the lignin arylamine macromolecular antioxidant of 0.1 part of synthesis and polypropylene machinery
After mixing, extrusion makes material (one section of temperature of barrel is 180 DEG C, two sections of temperature are 180 DEG C, three sections of temperature in double screw extruder
For 185 DEG C, four sections of temperature be 190 DEG C, die head temperature be 190 DEG C), standard batten then is made by injection machine in pellet,
Thermal-oxidative aging property test is carried out at 120 DEG C.
Comparative example 1
After 100 parts of natural rubbers on a mill thin logical 8 times, 2 parts of stearic acid, 5 parts of zinc oxide, 1.5 parts of promotions are added
Agent CZ, 0.5 part of altax and 1 part of alkali lignin, 30 parts of N330 carbon blacks are then added, are eventually adding 1.5 parts of sulphur, be kneaded
Slice obtains elastomeric compound after uniformly.Elastomeric compound parks after 24h that tabletting vulcanizes on 25 tons of hydraulic flat vulcanizers, curing temperature
For 143 DEG C, cure time 457s, the sample after vulcanization carried out after room temperature parks 24h accelerate thermo-oxidative ageing test and it is resistance to
Extracting test.
Comparative example 2
Other steps of this comparative example are identical with comparative example 1, and difference is：Alkali lignin changes N- phenyl into benzene two
Amine, corresponding cure time are 375s.
Comparative example 3
Other steps of this comparative example are identical with comparative example 1, and difference is：Alkali lignin changes p-phenylenediamine into, accordingly
Cure time is 375s.
Comparative example 4
By after 0.1 part of alkali lignin and polypropylene mechanical mixture, extruder temperature be 180 DEG C, 180 DEG C, 185 DEG C, 190
DEG C, 190 DEG C, 190 DEG C, extrusion makes material in 185 DEG C of double screw extruder, standard sample then is made by injection machine in pellet
Bar, thermo-oxidative ageing test is carried out at 120 DEG C.
Comparative example 5
Other steps of this comparative example are identical with comparative example 4, difference in：Any antioxidant is not added in polypropylene.
To be fully understood by the performance of various embodiments of the present invention and comparative example polymer samples, tensile strength has been carried out respectively
Tested with elongation at break test, heatproof air aging performance, as a result respectively as shown in table 1-2.
The thermo oxidative aging performance and resistant to extraction energy of the natural rubber vulcanized rubber of table 1
The polypropylene thermo oxidative aging performance of table 2
Note：RTSFor stretching strength retentivity, REBFor elongation at break conservation rate.
Characterizing method is as follows：
1st, the tensile strength of natural rubber and elongation at break test：Carried out by GB/T 528-2009.
2nd, the heatproof air aging performance test of natural rubber：Being carried out by GB/T 3512-2001, aging temperature is 100 DEG C,
Ageing time is 48h.
3rd, the solvent resistant extracting performance test of antioxidant：48h (methanol is changed per 24h once) is soaked in the methanol that seethes with excitement,
Then (100 DEG C × 48h) processing of hot oxygen accelerated ageing are carried out again.
4th, polyacrylic tensile strength and elongation at break test：GB/T1040-2006.
5th, polyacrylic heatproof air aging performance test：Carried out by GB/T 7141-2008, aging temperature is 120 DEG C, always
It is 2,4,6,8 days to change the time.
From table 1 it follows that the natural rubber for the lignin arylamine macromolecular antioxidant that 1 part of embodiment 1 of addition synthesizes
The tensile strength and elongation at break conservation rate of vulcanizate are respectively 76.4% and 72.1%, and after methanol extracts, it stretches strong
Degree and elongation at break conservation rate are respectively 73.2% and 75.9%, illustrate the lignin arylamine macromolecular of 1 synthesis of embodiment
Antioxidant has good thermo oxidative aging ability and solvent resistant extracting performance to natural rubber.Make with 1 part of alkali lignin of addition
(comparative example 1) is compared for antioxidant, the thermo oxidative aging effect for the lignin arylamine macromolecular antioxidant that embodiment 1 synthesizes is bright
It is aobvious to be better than lignin, illustrate that the introducing of arylamine enhances the antioxidant capacity of lignin；And with adding 1 part of 4-aminodiphenylamine
Make antioxidant and compare (comparative example 2), the solvent resistant extracting ability for the lignin arylamine macromolecular antioxidant that embodiment 1 synthesizes is bright
It is aobvious higher.
From table 1 it follows that addition 1 part of embodiment it is 2-in-1 into lignin arylamine macromolecular antioxidant natural rubber
The tensile strength and elongation at break conservation rate of vulcanizate are respectively 79.8% and 78.3%, and after methanol extracts, it stretches strong
Degree and elongation at break conservation rate are respectively 78.4% and 76.3%, illustrate that the lignin arylamine macromolecular that embodiment 2 synthesizes resists
Oxygen agent is more scattered in natural rubber, and natural rubber thermo oxidative aging ability and solvent resistant extracting performance are further improved
(compared with Example 1).
From table 1 it follows that the natural rubber for the lignin arylamine macromolecular antioxidant that 1 part of embodiment 3 of addition synthesizes
The tensile strength and elongation at break conservation rate of vulcanizate are respectively 80.4% and 79.3%, and after methanol extracts, it stretches strong
Degree and elongation at break conservation rate are respectively 79.2% and 78.4%, illustrate that the lignin arylamine macromolecular that embodiment 3 synthesizes resists
Oxygen agent has good thermo oxidative aging ability and solvent resistant extracting performance to natural rubber.
From table 1 it follows that the natural rubber for the lignin arylamine macromolecular antioxidant that 1 part of embodiment 4 of addition synthesizes
The tensile strength and elongation at break conservation rate of vulcanizate are respectively 83.1% and 84.7%, and after methanol extracts, it stretches strong
Degree and elongation at break conservation rate are respectively 81.2% and 80.5%, (right compared with adding 1 part of p-phenylenediamine as antioxidant
Ratio 3), lignin arylamine macromolecular antioxidant thermo oxidative aging ability and solvent resistant the extracting performance that embodiment 4 synthesizes are obvious
It is better than p-phenylenediamine.
Obtained polypropylene thermal-oxidative aging property is shown in Table 2 in embodiment 5.From Table 2, it can be seen that contain 0.1 part of embodiment
The polypropylene of the lignin arylamine macromolecular antioxidant of 5 synthesis is in 120 DEG C of thermo-oxidative ageings, 8 days post-tensioning strength retentions and breaks
It is respectively 94.1% and 91.2% to split percent retention of elongation, illustrates the lignin arylamine macromolecular antioxidant pair that embodiment 5 synthesizes
Polypropylene has good thermo oxidative aging ability, and significantly better than the antioxidant effect (comparative example 4) of lignin.
The thermo oxidative aging performance of the natural rubber vulcanized rubber containing lignin and resistant to extraction can be shown in Table 1 in comparative example 1.
From table 1 it follows that the tensile strength and elongation at break conservation rate of the natural rubber vulcanized rubber of 1 part of alkali lignin of addition
It is only respectively 53.2% and 56.5%, after methanol extracts, its tensile strength and elongation at break conservation rate are respectively 52.4%
With 55.3%, illustrate that lignin is poor as natural rubber antioxidant effect.
The thermo oxidative aging performance and resistant to extraction of natural rubber vulcanized rubber containing 4-aminodiphenylamine in comparative example 2
1 can be shown in Table.From table 1 it follows that add the tensile strength of the natural rubber vulcanized rubber of 1 part of 4-aminodiphenylamine and break
It is respectively 73.2% and 74.7% to split percent retention of elongation, after methanol extracts, its tensile strength and elongation at break conservation rate
Respectively 57.1% and 58.9%, illustrate that 4-aminodiphenylamine has preferable oxidation resistance, but solvent resistant to natural rubber
Extraction effect is poor.
The thermo oxidative aging performance of the natural rubber vulcanized rubber containing p-phenylenediamine and resistant to extraction can be shown in Table in comparative example 3
1.From table 1 it follows that the tensile strength and elongation at break of the natural rubber vulcanized rubber of 1 part of p-phenylenediamine of addition are kept
Rate is respectively 77.4% and 75.6%, and after methanol extracts, its tensile strength and elongation at break conservation rate are respectively 55.3%
With 50.4%, illustrate that p-phenylenediamine has preferable oxidation resistance to natural rubber, but solvent resistant extraction effect is poor.
Polyacrylic thermal-oxidative aging property is shown in Table 2 in comparative example 4.It is from Table 2, it can be seen that poly- containing 0.1 part of lignin
Propylene is respectively 86.3% and 90.3% in the old 8 days post-tensioning strength retentions of 120 DEG C of hot oxygen and elongation at break conservation rate,
Illustrate that lignin has certain thermo oxidative aging ability to polypropylene, but be not so good as lignin aromatic amine macromolecular antioxygen.
Polyacrylic thermal-oxidative aging property is shown in Table 2 in comparative example 5.From Table 2, it can be seen that polypropylene is in 120 DEG C of hot oxygen
8 days post-tensioning strength retentions of aging and elongation at break conservation rate are respectively 41.1% and 31.0%, illustrate that polypropylene is easy
Thermo-oxidative ageing.
Claims (10)
1. a kind of multi-functional lignin arylamine macromolecular antioxidant, it is characterised in that the structure of the novel antioxidant is as follows：
Wherein, R1Selected from hydrogen or methoxyl group, R2It is selected from In one kind.
2. the preparation method of multi-functional lignin arylamine macromolecular antioxidant described in claim 1, it is characterised in that including with
Lower step：(a) with water as solvent, lignin, arylamine are mixed in proportion, regulation pH value of solution to alkalescence；(b) protective atmosphere
Under, formaldehyde, temperature reaction are added into mixed solution；(c) mixed solution pH is adjusted after the completion of reacting to acidity, continues to heat up,
Filtered after luming, washing is dried to obtain lignin arylamine macromolecular antioxidant.
3. the preparation method of multi-functional lignin arylamine macromolecular antioxidant as claimed in claim 2, it is characterised in that：Wood
Mass ratio when quality, arylamine, water mixing is 100：10~150：400~900.
4. the preparation method of multi-functional lignin arylamine macromolecular antioxidant as claimed in claim 2, it is characterised in that：First
The addition of aldehyde is (6-12) % of lignin quality.
5. the preparation method of multi-functional lignin arylamine macromolecular antioxidant as claimed in claim 2, it is characterised in that：Instead
Ying Qianyong sodium hydrate regulator solutions pH to 10.5-12, pH value of solution is adjusted to 2-3 with dilute sulfuric acid after reaction.
6. the preparation method of multi-functional lignin arylamine macromolecular antioxidant as claimed in claim 2, it is characterised in that：Instead
45-80 DEG C of temperature is answered, hour in reaction time 1-3, has reacted and mixed solution pH is adjusted to acidity, is warming up to 80-90 DEG C, after caking
Filter and multiple with hot wash, then washed with absolute ethyl alcohol, product finally is placed in into 60 DEG C of environment vacuums dries 24 hours
Produce.
7. the preparation method of the multi-functional lignin arylamine macromolecular antioxidant as described in claim any one of 2-6, it is special
Sign is：The lignin be alkali lignin, sulfate-reducing conditions, enzymolysis xylogen, acetic acid lignin, high-boiling alcohol lignin,
Acetone lignin, ammonia lignin, phenol lignin, ionic liquid lignin, explosion lignin, supercritical extract lignin and molten
Any one or more mixture formed in formulation lignin.
8. the preparation method of the multi-functional lignin arylamine macromolecular antioxidant as described in claim any one of 2-6, it is special
Sign is：The arylamine is any one or more formation in aniline, p-phenylenediamine, diphenylamines, 4-aminodiphenylamine
Mixture.
9. the application of multi-functional lignin arylamine macromolecular antioxidant in the polymer described in claim 1, it is characterised in that：
According to 0.1-3:Obtained lignin arylamine macromolecular antioxidant is added in polymer by 100 mass ratio to be well mixed, institute
Stating polymer includes natural rubber, butadiene-styrene rubber, nitrile rubber, butadiene rubber, polypropylene, and antioxidant addition manner includes and rubber
Glue is directly kneaded, is blended with rubber latex blending, with polypropylene fusion.
10. the application of multi-functional lignin arylamine macromolecular antioxidant in the polymer as claimed in claim 9, its feature
It is：
Method of the lignin arylamine macromolecular antioxidant directly with compounding rubber be specially：Rubber it is thin it is logical after, add stearic acid, oxygen
Change zinc, accelerant CZ, altax and lignin arylamine macromolecular antioxidant and be kneaded uniformly, then add carbon black and sulphur
Sulphur, slice after being kneaded uniformly, obtains the elastomeric compound containing lignin arylamine macromolecular antioxidant, parks after cure；
The method that lignin arylamine macromolecular antioxidant is blended with rubber latex is specially：By lignin arylamine macromolecular antioxidant
It is added in 0.1mol/L sodium hydroxide solution, is configured to the antioxidant solution of 10% solid content, antioxidant solution is added
Into the rubber latex of solid content 60%, it is uniformly mixed, is then demulsified and is washed with deionized with 1mol/L watery hydrochloric acid,
The rubber raw rubber of the macromolecular antioxidant of arylamine containing lignin is dried to obtain, is finally kneaded and vulcanizes according to preceding method；
Lignin arylamine macromolecular antioxidant is specially with polypropene blended method：Lignin arylamine macromolecular is resisted at room temperature
Oxygen agent and polypropylene mechanical mixture are uniform, then the extruding pelletization in double screw extruder, and extrusion temperature is 180-200 DEG C, most
Afterwards by pellet injection molding, injection temperature is 190 DEG C.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111004669A (en) * | 2019-12-11 | 2020-04-14 | 中国科学院兰州化学物理研究所 | Ionic liquid lignin lubricating composition and preparation method and application thereof |
| CN111187471A (en) * | 2020-02-25 | 2020-05-22 | 爱康企业集团(上海)有限公司 | Anti-aging fresh air pipe and preparation method thereof |
| CN111393669A (en) * | 2020-05-22 | 2020-07-10 | 江西宝弘纳米科技有限公司 | Long-acting anti-aging agent and preparation method and application thereof |
| CN111892716A (en) * | 2020-07-23 | 2020-11-06 | 青岛科技大学 | Lignin-based multifunctional rubber additive and preparation method and application thereof |
| CN113637245A (en) * | 2021-08-16 | 2021-11-12 | 深圳市峰源化工新材料股份有限公司 | Lignin modified styrene butadiene rubber thermoplastic elastomer and preparation method thereof |
| CN113980355A (en) * | 2021-11-24 | 2022-01-28 | 中胶永生东南亚乳胶制品股份有限公司 | Multifunctional rubber additive and preparation method thereof |
| CN115512978A (en) * | 2022-09-27 | 2022-12-23 | 武汉工程大学 | Flexible electrochemical energy storage device and preparation method thereof |
| CN115716921A (en) * | 2022-11-28 | 2023-02-28 | 南京工业大学 | Bio-based anti-aging agent and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013031039A1 (en) * | 2011-09-02 | 2013-03-07 | ハリマ化成株式会社 | Modified lignin and phenolic resin molding material containing same |
| CN104693450A (en) * | 2013-12-04 | 2015-06-10 | 青岛惠城石化科技有限公司 | Tetraethylenepentamine/ formaldehyde modified lignin-amine asphalt emulsifier synthetic process |
| CN106589403A (en) * | 2016-11-10 | 2017-04-26 | 广西大学 | Method for improving anti-oxidation activity of lignin through degradation with laccase |
-
2017
- 2017-11-09 CN CN201711108513.4A patent/CN107892752B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013031039A1 (en) * | 2011-09-02 | 2013-03-07 | ハリマ化成株式会社 | Modified lignin and phenolic resin molding material containing same |
| CN104693450A (en) * | 2013-12-04 | 2015-06-10 | 青岛惠城石化科技有限公司 | Tetraethylenepentamine/ formaldehyde modified lignin-amine asphalt emulsifier synthetic process |
| CN106589403A (en) * | 2016-11-10 | 2017-04-26 | 广西大学 | Method for improving anti-oxidation activity of lignin through degradation with laccase |
Non-Patent Citations (3)
| Title |
|---|
| 关丽珠: ""木质素的胺化及其固化环氧树脂的研究"", 《中国优秀硕士学位论文全文数据库工程科技I辑》 * |
| 张晓阳等主编: "《纤维素生物质水解与应用》", 31 December 2012, 郑州大学出版社 * |
| 马艳丽编著: "《喹啉方酸菁/二氧化钛的制备及其活化碱木质素的研究》", 30 August 2012, 东北林业大学出版社 * |
Cited By (8)
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|---|---|---|---|---|
| CN111004669A (en) * | 2019-12-11 | 2020-04-14 | 中国科学院兰州化学物理研究所 | Ionic liquid lignin lubricating composition and preparation method and application thereof |
| CN111187471A (en) * | 2020-02-25 | 2020-05-22 | 爱康企业集团(上海)有限公司 | Anti-aging fresh air pipe and preparation method thereof |
| CN111393669A (en) * | 2020-05-22 | 2020-07-10 | 江西宝弘纳米科技有限公司 | Long-acting anti-aging agent and preparation method and application thereof |
| CN111892716A (en) * | 2020-07-23 | 2020-11-06 | 青岛科技大学 | Lignin-based multifunctional rubber additive and preparation method and application thereof |
| CN113637245A (en) * | 2021-08-16 | 2021-11-12 | 深圳市峰源化工新材料股份有限公司 | Lignin modified styrene butadiene rubber thermoplastic elastomer and preparation method thereof |
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| CN115716921A (en) * | 2022-11-28 | 2023-02-28 | 南京工业大学 | Bio-based anti-aging agent and preparation method and application thereof |
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