CN107163227B - Using bark as epoxy hardener of raw material and preparation method thereof - Google Patents
Using bark as epoxy hardener of raw material and preparation method thereof Download PDFInfo
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- CN107163227B CN107163227B CN201710383170.6A CN201710383170A CN107163227B CN 107163227 B CN107163227 B CN 107163227B CN 201710383170 A CN201710383170 A CN 201710383170A CN 107163227 B CN107163227 B CN 107163227B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/64—Amino alcohols
Abstract
Using bark as epoxy hardener of raw material and preparation method thereof, first bark is smashed it through and is mixed with alkali after 40 meshes, after keeping the temperature 2 ~ 4 hours at 90 DEG C, after filtering residue, obtains bark extract after liquid is spray-dried；Bark extract and formaldehyde, polyamines carry out Mannich condensation reaction and a kind of Mannich base curing agent can be obtained；Or react bark extract with maleic anhydride with epoxide prepared by epichlorohydrin reaction, a kind of acids curing agent can be obtained；Or react bark extract with polyamine with epoxide prepared by epichlorohydrin reaction, a kind of amine curing agent can be obtained.The bark for selecting natural reproducible resource is that raw material prepares epoxy hardener product, is conducive to the high value added utilization for pushing the renewable agriculture and forestry resource of green, has complied with environmentally protective and sustainable development requirement.
Description
Technical field
The invention belongs to epoxy hardener fields, and in particular to using bark as the epoxy hardener of raw material and its preparation side
Method.
Background technique
Epoxy resin is that one kind applies very extensive thermosetting material in national product life.However epoxy resin sheet
Body is a kind of thermoplastic resin material, and since its molecular structure is linearly distributed, heated rear solid resin can show soft
Change, the state of melting, liquid resin its viscosity that is heated can then reduce, therefore in practical applications, simple epoxy resin is without very
Big practical value is only allowed to form the high polymerization of tridimensional network after curing agent and some other altered contents are added
Object material can just access a series of excellent physical mechanical properties.
Currently used epoxy curing agent is broadly divided into two major classes, including shows in type curing agent and resting form solidification
Agent, wherein showing in type curing agent mainly includes polynary amine, anhydride, polymercaptan and poly- phenol etc..At this stage amine curing agent and
The application of acid anhydride type curing agent in the epoxy is very universal.Polyamine and acid anhydride type curing agent currently used in the market are big
All be petroleum-based products, and petroleum resources have it is non-renewable, it is long-term using not meeting China's strategy of sustainable development.Cause
This, greatly develops biological based epoxy curing agent, by the MOLECULE DESIGN to bio-based polymers material, makes energy portion
Dividing even is all the hot spot direction studied at this stage instead of the polymer of petroleum-based products.
Lignin is the main scrap feed material in pulp and paper industry, is applied to synthesis mechanical performance and thermostabilization
The preferable Lignin-based epoxy resin of property.However, the molecular weight ranges of lignin are from 2000~50000Da, this will lead to wood
Quality base epoxy viscosity is larger, not easy to use.Contain a large amount of lignin and polyphenols compound (42~55%) in bark,
And the polyphenolic substance containing a large amount of low molecular weight in the polyphenolic substance contained in bark.In addition, compared with lignin, bark
The extraction of middle polyphenolic substance is relatively simple, less energy intensive.
China's wood residue resource very abundant, up to nearly hundred million tons.Then, the bark in wood residue resource at present
It is still very low using level, in addition to being used for fuel and raw material of artifical plate on a small quantity, mostly as garbage disposal.In bark powder
Polyphenolic substance can be extracted by the method for alkali process, can using the epoxy hardener product that bark powder is produced as raw material
Part substitution petroleum-based epoxy curing agent product, is to realize extensive, high-quality, high value added utilization Woody plant resource most
One of effective ways.
Summary of the invention
The technical issues of solution: the present invention, for raw material, is provided a kind of solid by the epoxy of raw material of bark with bark powder etc.
Agent and preparation method thereof, the product is alternative or part substitutes petroleum-based epoxy curing agent.
Technical solution: using bark as the preparation method of the epoxy hardener of raw material, preparation step are as follows: (1) prepare bark and mention
Take object: bark process is dried, grinding and sieving obtains bark powder, by bark powder, alkali and water by weight 1:(8~15): (0~
150) ratio after mixing, keeps the temperature 2~4 hours at 90~100 DEG C, through filtering residue, after liquid is spray-dried
To bark extract；(2) choose any one kind of them from following A, B, step C, prepare epoxy hardener: in proportion, bark is extracted by A.
Object 4.6g, 5.2~11.5g polyamine after mixing, are warming up to 80 DEG C, and the 37wt.% of 8g~12g is added dropwise in 30min
Formalin after reacting 4~6h, is warming up to 120 DEG C of extra moisture of removal, obtains epoxy hardener；B. in proportion, by benzyl
Any one in triethyl ammonium chloride 0.5g or tetrabutylammonium hydroxide 12.5mL, with bark extract 90g, epoxychloropropane
900g and Isosorbide-5-Nitrae-dioxane 900g are mixed, and 6~8h are sufficiently stirred after being warming up to 60~75 DEG C, then temperature is down to 60 DEG C, adds
Enter 8~40g sodium hydroxide and 1~12.0g calcium oxide, after stirring 5~9h, acetone 500mL is added into mixture, is filtered to remove
Solid salt, then acetone and excessive epoxychloropropane are recycled through vacuum distillation, finally obtain a kind of bark powder source epoxy compound
Object Bark-epoxy；By Bark-epoxy 30g, 1,4- dioxane 30g and 19~21g of maleic anhydride after mixing in 110
1.5~3h is reacted at~120 DEG C, obtains epoxy hardener；C. in proportion, above-mentioned Bark-epoxy 30g, Isosorbide-5-Nitrae-dioxane are taken
30g reacts 3.5~5h at 60~80 DEG C after mixing with 20~45g of polyamine, obtains a kind of epoxy hardener.
Alkali described in (1) step is NaOH, KOH, any one in organic amine.
Bark described in (1) step is selected from shore pipe bark, Masson Pine Bark, Korean pine bark, bark of dahurian larch etc.
In any one.
Polyamine described in organic amine and (2) step in (1) step is selected from ethylenediamine, diethylenetriamine, triethylene
At least one of tetramine, aminoethyl piperazine, polyetheramine D230,3,3 '-diamino di-n-propylamines.
Epoxy hardener made from the above method.
The utility model has the advantages that 1. containing the polyphenolic substance of a large amount of low molecular weights, compared with lignin, polyphenol in bark in bark
The extraction of compound is relatively simple, less energy intensive.2. the present invention is with wooden using the epoxy hardener product that bark is prepared as raw material
Element and the polyphenolic substance of low molecular weight are basic framework, are the Related products such as the epoxy resin of basic framework with common lignin
It compares, molecular weight is smaller, convenient for the technological operation of later period synthetic epoxy resin curing agent.3. selecting bark powder for raw material preparation
Epoxy hardener product is conducive to the high value added utilization for pushing the renewable agriculture and forestry resource of green, complied with it is environmentally protective with
The requirement of sustainable development.
Specific embodiment
Part is not directed in text to be the same as those in the prior art or can be realized by using the prior art.Following is the present invention
Preferred embodiment, but the present invention is also not limited to following only embodiment, is slightly modified also in embodiment and will be regarded as this
The protection scope of invention.
Embodiment 1
The first step, shore pipe bark obtains bark powder by drying, smashing it through 40 meshes, by bark powder and NaOH and water
By weight 1:9:90 ratio after mixing, in 95 DEG C keep the temperature 3 hours, filter residue, obtained after liquid is spray-dried
Bark extract.
Second step, by bark extract 90g, epoxychloropropane 900g, Isosorbide-5-Nitrae-dioxane 900g and benzyl triethyl ammonium chlorine
Change ammonium 0.5g to be added in the three-necked flask equipped with mechanical stirring paddle, thermometer and reflux condensing tube, sufficiently be stirred after being warming up to 75 DEG C
6h is mixed, then temperature is down to 60 DEG C of addition 20g sodium hydroxides and 12g calcium oxide, and after stirring 9h, acetone is added in mixture
It is filtered to remove solid salt after 500mL dilution, then acetone and excessive epoxychloropropane are obtained into one kind after vacuum distillation recycling
Bark powder source epoxide (Bark-epoxy).Take Bark-epoxy (30g), 1,4- dioxane (30g) and triethylene four
Amine (14.6g), aminoethyl piperazine (13g) in 60 DEG C of reaction 5h, obtain a kind of amine curing agent after mixing.
Embodiment 2
The first step, Masson Pine Bark obtain bark powder by drying, smashing it through 40 meshes, bark powder and KOH and water are pressed
The ratio of weight ratio 1:10:100 keeps the temperature 3 hours after mixing, in 100 DEG C, filters residue, obtains after liquid is spray-dried
Bark extract.
Bark extract is added in the 500mL three-necked flask equipped with mechanical stirring, water segregator and thermometer in second step
4.6g, 6.5g aminoethyl piperazine after mixing, are warming up to 80 DEG C, in 30min by 37% formalin of 12g be added dropwise into
It goes, after reacting 6h, extra moisture can be collected in water segregator by being warming up to 120 DEG C, obtain a kind of Mannich base curing agent.
Embodiment 3
The first step, Korean pine bark obtain bark powder by drying, smashing it through 40 meshes, by weight with ethylenediamine by bark powder
Ratio than 1:15 keeps the temperature 3 hours after mixing, in 95 DEG C, filters residue, and bark extraction is obtained after liquid is spray-dried
Object.
Second step, by bark extract 90g, epoxychloropropane 900g, Isosorbide-5-Nitrae-dioxane 900g and tetrabutylammonium hydroxide
Ammonium 12.5mL is added in the three-necked flask equipped with mechanical stirring paddle, thermometer and reflux condensing tube, sufficiently stirs after being warming up to 60 DEG C
7h is mixed, then temperature is down to 60 DEG C of addition 40g sodium hydroxides and 1g calcium oxide, and after stirring 5h, acetone 500mL is added in mixture
It is filtered to remove solid salt after dilution, then acetone and excessive epoxychloropropane are obtained into a kind of bark after vacuum distillation recycling
Powder source epoxide (Bark-epoxy).Take Bark-epoxy (30g), 1,4- dioxane (30g) and diethylenetriamine 20g
After mixing in 70 DEG C of reaction 5h, a kind of amine curing agent is obtained.
Embodiment 4
The first step, bark of dahurian larch obtain bark powder by drying, smashing it through 40 meshes, bark powder and NaOH and water are pressed
The ratio of weight ratio 1:12:120 keeps the temperature 2 hours after mixing, in 100 DEG C, filters residue, obtains after liquid is spray-dried
Bark extract.
Second step, by bark extract 90g, epoxychloropropane 900g, Isosorbide-5-Nitrae-dioxane 900g and tetrabutylammonium hydroxide
Ammonium 12.5mL is added in the three-necked flask equipped with mechanical stirring paddle, thermometer and reflux condensing tube, sufficiently stirs after being warming up to 60 DEG C
6h is mixed, then temperature is down to 60 DEG C of addition 15g sodium hydroxides and 10g calcium oxide, and after stirring 5h, acetone is added in mixture
It is filtered to remove solid salt after 500mL dilution, then acetone and excessive epoxychloropropane are obtained into one kind after vacuum distillation recycling
Bark powder source epoxide (Bark-epoxy).Bark-epoxy (30g), 1,4- dioxane (30g) and maleic anhydride
(20g) in 115 DEG C of reaction 2h, obtains a kind of acids curing agent after mixing.
Embodiment 5
The first step, shore pipe bark obtains bark powder by drying, smashing it through 40 meshes, by bark powder and NaOH, KOH
After mixing, 4 hours are kept the temperature at 90 DEG C with the ratio of 1:8:80 by weight of water, filters residue, liquid is through spraying dry
Bark extract is obtained after dry.
Bark extract is added in the 500mL three-necked flask equipped with mechanical stirring, water segregator and thermometer in second step
4.6g, 11.5g polyetheramine D230 after mixing, are warming up at 80 DEG C, and 37% formalin of 10g is added dropwise in 30min
Enter, after reacting 5h, extra moisture can be collected in water segregator by being warming up to 120 DEG C, obtain a kind of Mannich base curing agent.
Embodiment 6
The first step, the shore pipe bark powder by drying, smashing it through 40 meshes, bark powder and NaOH, KOH and water
The ratio by weight 1:8:80 after mixing, after keep the temperature 3 hours at 95 DEG C, filtering residue, liquid is spray-dried
After obtain bark extract.
Second step, by bark extract 90g, epoxychloropropane 900g, Isosorbide-5-Nitrae-dioxane 900g and tetrabutylammonium hydroxide
Ammonium 12.5mL is added in the three-necked flask equipped with mechanical stirring paddle, thermometer and reflux condensing tube, sufficiently stirs after being warming up to 60 DEG C
7h is mixed, then temperature, which is down at 60 DEG C, is added 40g sodium hydroxide and 1g calcium oxide, and after stirring 5h, acetone is added in mixture
It is filtered to remove solid salt after 500mL dilution, then acetone and excessive epoxychloropropane are obtained into one kind after vacuum distillation recycling
Bark powder source epoxide (Bark-epoxy).Take Bark-epoxy (30g), 1,4- dioxane (30g), ethylenediamine 5.8g
5h is reacted at 70 DEG C after mixing with triethylene tetramine 14.2g, obtains a kind of amine curing agent.
Embodiment 7
The first step, the shore pipe bark powder by drying, smashing it through 40 meshes, bark powder and NaOH, KOH and water
The ratio by weight 1:8:80 after mixing, after keep the temperature 3 hours at 95 DEG C, filtering residue, liquid is spray-dried
After obtain bark extract.
Second step, by bark extract 90g, epoxychloropropane 900g, Isosorbide-5-Nitrae-dioxane 900g and tetrabutylammonium hydroxide
Ammonium 12.5mL is added in the three-necked flask equipped with mechanical stirring paddle, thermometer and reflux condensing tube, sufficiently stirs after being warming up to 60 DEG C
7h is mixed, then temperature, which is down at 60 DEG C, is added 40g sodium hydroxide and 1g calcium oxide, and after stirring 5h, acetone is added in mixture
It is filtered to remove solid salt after 500mL dilution, then acetone and excessive epoxychloropropane are obtained into one kind after vacuum distillation recycling
Bark powder source epoxide (Bark-epoxy).Take Bark-epoxy (30g), 1,4- dioxane (30g) and 3,3 '-diaminos
Base di-n-propylamine 25.5g reacts 4h at 70 DEG C after mixing, obtains a kind of amine curing agent.
Embodiment 8
By the obtained amine curing agent 50g of embodiment 1,50 type curing agent (amine value 210mg/g) 102g of polyamide 6 and
325g epoxy resin 618 (epoxide number 0.51) is blended uniformly, and the mode of temperature programming is taken to carry out solidified sample, condition of cure
Are as follows: 80 DEG C/2h+120 DEG C/1h+175 DEG C/2h, obtain cured product 477g.
Embodiment 9
By the obtained Mannich base curing agent 50g of embodiment 2, polyamide 6 50 type curing agent (amine value 210mg/g) 153g
It is blended uniformly with 412g epoxy resin 128 (epoxide number 0.51), the mode of temperature programming is taken to carry out solidified sample, condition of cure
Are as follows: 80 DEG C/2h+120 DEG C/1h+175 DEG C/2h, obtain cured product 615g.
Embodiment 10
By the obtained acids curing agent 50g of embodiment 4,50 type curing agent (amine value 210mg/g) 51g of polyamide 6 and
215g epoxy resin 128 (epoxide number 0.51) and 0.15g altax P-30 are blended uniformly, and the mode of temperature programming is taken to carry out
Solidified sample, condition of cure are as follows: 80 DEG C/2h+120 DEG C/1h+175 DEG C/2h, obtain cured product 165g.
Embodiment 11
By the obtained Mannich base curing agent 20g of embodiment 5, polyamide 6 50 type curing agent (amine value 210mg/g) 204g
It is blended uniformly with 432g epoxy resin 128 (epoxide number 0.51), the mode of temperature programming is taken to carry out solidified sample, condition of cure
Are as follows: 80 DEG C/2h+120 DEG C/1h+175 DEG C/2h, obtain cured product 734g.
Comparative example 1
Polyamide 6 50 type curing agent (amine value 210mg/g) 51g and (epoxide number 0.51) 100g of epoxy resin 128 are blended
Uniformly, the mode of temperature programming is taken to carry out solidified sample, condition of cure are as follows: 80 DEG C/2h+120 DEG C/1h+175 DEG C/2h, must consolidate
Change product 151g.
Curing agent measures its amine value by national standard GB/T 9736-88 in above-described embodiment and comparative example.Above-described embodiment and ratio
Cured product compared with curing agent in example measures its tensile strength and elasticity modulus by ASTM D-638.
1 embodiment and comparative example performance comparison of table
| Formula | Tensile strength (MPa) | Elasticity modulus (MPa) |
| Embodiment 8 | 34.5 | 1205.6 |
| Embodiment 9 | 35.6 | 1357.2 |
| Embodiment 10 | 35.8 | 1550.5 |
| Embodiment 11 | 38.6 | 1900.3 |
| Comparative example 1 | 36.0 | 1913.2 |
Claims (5)
1. using bark as the preparation method of the epoxy hardener of raw material, it is characterised in that preparation step are as follows:
(1) prepare bark extract: bark process is dried, grinding and sieving obtains bark powder, by weight by bark powder, alkali and water
1:(8 ~ 15): the ratio of (0 ~ 150) after mixing, keeps the temperature 2 ~ 4 hours at 90 ~ 100 DEG C, and through filtering residue, liquid is through spraying
Bark extract is obtained after mist is dry；
(2) it chooses any one kind of them from following A, B, step C, prepares epoxy hardener:
A. in proportion, after mixing by 4.6 g of bark extract, 5.2 ~ 11.5 g polyamines, 80 DEG C are warming up to, and 30
The 37 wt.% formalins of the g of 8 g ~ 12 are added dropwise in min, after reacting 4 ~ 6 h, are warming up to 120 DEG C of extra moisture of removal,
Obtain epoxy hardener；
B. in proportion, by any one in 12.5 mL of 0.5 g of benzyltriethylammoinium chloride or tetrabutylammonium hydroxide, with tree
90 g of bark extract, 900 g of epoxychloropropane and 900 g of Isosorbide-5-Nitrae-dioxane are mixed, and are sufficiently stirred after being warming up to 60 ~ 75 DEG C
6 ~ 8 h are mixed, then temperature is down to 60 DEG C, 8 ~ 40 g sodium hydroxides and 1 ~ 12.0 g calcium oxide is added, after stirring 5 ~ 9 h, to
500 mL of acetone is added in mixture, is filtered to remove solid salt, then acetone and excessive epoxychloropropane are evaporated under reduced pressure back
It receives, finally obtains a kind of bark powder source epoxide Bark-epoxy；By 30 g, 1,4- dioxane 30 of Bark-epoxy
G and 19 ~ 21 g of maleic anhydride reacts 1.5 ~ 3 h at 110 ~ 120 DEG C after mixing, obtains epoxy hardener；
C. in proportion, above-mentioned 30 g of Bark-epoxy, 30 g of Isosorbide-5-Nitrae-dioxane is taken to be uniformly mixed with 20 ~ 45 g of polyamine
3.5 ~ 5 h are reacted at 60 ~ 80 DEG C afterwards, obtain a kind of epoxy hardener.
2. according to claim 1 using bark as the preparation method of the epoxy hardener of raw material, it is characterised in that (1) step
Described in alkali be NaOH, KOH, any one in organic amine.
3. according to claim 1 using bark as the preparation method of the epoxy hardener of raw material, it is characterised in that (1) step
Described in any one in shore pipe bark, Masson Pine Bark, Korean pine bark, bark of dahurian larch of bark.
4. according to claim 2 using bark as the preparation method of the epoxy hardener of raw material, it is characterised in that (1) step
In organic amine and (2) step described in polyamine be selected from ethylenediamine, diethylenetriamine, triethylene tetramine, aminoethyl piperazine,
At least one of polyetheramine D230,3,3 '-diamino di-n-propylamines.
5. epoxy hardener made from any the method for claim 1 ~ 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710383170.6A CN107163227B (en) | 2017-05-26 | 2017-05-26 | Using bark as epoxy hardener of raw material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710383170.6A CN107163227B (en) | 2017-05-26 | 2017-05-26 | Using bark as epoxy hardener of raw material and preparation method thereof |
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| CN107163227A CN107163227A (en) | 2017-09-15 |
| CN107163227B true CN107163227B (en) | 2019-03-26 |
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| CN201710383170.6A Active CN107163227B (en) | 2017-05-26 | 2017-05-26 | Using bark as epoxy hardener of raw material and preparation method thereof |
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Families Citing this family (1)
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| CN108586710B (en) * | 2018-05-17 | 2020-09-01 | 中国林业科学研究院林产化学工业研究所 | Woody vegetable oil fat based multi-element polyamide epoxy curing agent and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA815588A (en) * | 1969-06-17 | G. Allan George | Resin hardeners derived from bark phenolic acids | |
| US3472797A (en) * | 1968-01-30 | 1969-10-14 | Weyerhaeuser Co | Epoxy resin hardeners derived from aqueous alkali-extracted bark phenolic acids |
| US3511874A (en) * | 1968-04-23 | 1970-05-12 | Weyerhaeuser Co | Esters of bark phenolic acids |
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