CN108997615A - A kind of piperazine modified lignin resin/aluminium hydroxide dual cladding red phosphorus combustion inhibitor and its application in EVA - Google Patents
A kind of piperazine modified lignin resin/aluminium hydroxide dual cladding red phosphorus combustion inhibitor and its application in EVA Download PDFInfo
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- CN108997615A CN108997615A CN201810899929.0A CN201810899929A CN108997615A CN 108997615 A CN108997615 A CN 108997615A CN 201810899929 A CN201810899929 A CN 201810899929A CN 108997615 A CN108997615 A CN 108997615A
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- red phosphorus
- lignin
- piperazine
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- aluminium hydroxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K2003/026—Phosphorus
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
The invention discloses a kind of piperazine modified lignin resin/aluminium hydroxide dual cladding red phosphorus combustion inhibitor and its applications in EVA, belong to high molecular material additive agent field.Based on the mass percent of each component, core material 15%-35% in fire retardant, shell material 65%-85%；Core material is red phosphorus (10-30%), shell material L-P(45-65%) and aluminium hydroxide (10-30%).For the present invention using biological material lignin as the charcoal source raw material of fire retardant, piperazine is the gas source raw material of fire retardant, and piperazine is grafted on lignin molecule by Mannich reaction and forms network-like macromolecular；Red phosphorus is then added in the solution as the gas source and aluminium salt of fire retardant, reversed co-precipitation occurs, the piperazine modified lignin resin/aluminium hydroxide dual cladding red phosphorus combustion inhibitor is made.Fire retardant partial size obtained by the present invention is smaller, good stability of the dimension, the compatibility that can be effectively improved between fire retardant and basis material.
Description
Technical field
The invention belongs to high molecular material additive technology fields, and in particular to a kind of piperazine modified lignin resin/hydroxide
Aluminium dual cladding red phosphorus combustion inhibitor and its application in EVA.
Background technique
In recent years, a large amount of uses of halogen containing flame-retardant have seriously endangered Environmental security and human health, more and more
Researcher is dedicated to developing novel halogen-free flame-retardant agent.Red phosphorus is a kind of tradition and efficient halogen-free flame retardants.However, without
The red phosphorus for crossing surface treatment is extremely unstable in air, can react with steam and generate highly toxic PH3, and and matrix
Poor compatibility, the processing difficulties of material.Current solution mainly carries out red phosphorus micro mist with organic and inorganic matter to it
Surface containment improves compatibility to completely cut off moisture.This microencapsulated powder oil has very high moisture resistance, preferable flowing
Property, longer storage time and less PH3It generates.In the preparation process of microencapsulated powder oil, suitable shell material is to determine
An important factor for flame retardant property.Biological material is renewable, carbon content is high, causes the concern of researcher.It is universal in plant
Existing lignin contains a large amount of active group, such as hydroxyl, methoxyl group and ehter bond in structure, not only lignin is had
For the possibility of a variety of chemical modifications, and fine and close layer of charcoal can be generated in combustion.
Some metal hydroxides such as magnesium hydroxide and aluminum trihydrate etc. are also furtherd investigate as halogen-free flame retardants.This
A little inorganic metal hydroxide can play a role in condensed phase and gas phase, and decompose after the endothermic reaction, reduce macromolecule
Steam is simultaneously discharged into gas phase by the rate of heat addition of material, and the oxygen concentration in dilute combustion region is to delay burning.In addition,
Surface of polymer material is condensed in after the metal hydroxides that burning generates is cooling, forms the protective layer of insulating, this is also helped
In high molecular fire retardant.Especially aluminum trihydrate causes more concerns as a kind of anacidity, Halogen, smoke inhibition fire retardant.But
Aluminum trihydrate additive amount when being used alone is more than that 60 wt% can be only achieved ideal flame retardant rating.Therefore, using lignin as
The charcoal source of halogen-free expansion fire retardant is reacted by Mannich and is grafted to form three-dimensional network-like structure and coat with piperazine moieties
Red phosphorus micro mist prepares Novel wooden quality base microencapsulated red phosphorus flame retardant, while introducing aluminium hydroxide conduct during the preparation process
Inorganic matter capsule material and fire retarding synergist achieve the effect that organic and inorganic dual cladding red phosphorus, can give full play to the excellent of each component
Gesture is complementary to one another, and plays synergistic effect.
Summary of the invention
The purpose of the present invention is to provide a kind of piperazine modified lignin resin/aluminium hydroxide dual cladding red phosphorus combustion inhibitor and its
Application in EVA, using biological material lignin as the charcoal source raw material of fire retardant, piperazine is the gas source raw material of fire retardant, is led to
Mannich reaction is crossed piperazine is grafted on lignin molecule to form network-like macromolecular；Red phosphorus is then added in the solution to make
Reversed co-precipitation occurs for the gas source and aluminium salt of fire retardant, the piperazine modified lignin resin/aluminium hydroxide for being made described is double
Weight Wrapped up Phosphorus Fire Retardant.Current halogen-free flame retardants can effectively be solved the EVA the technical issues of, mentioned for microencapsulated powder oil technology
For a kind of raw material green, preparation cost is cheap, flame retarding efficiency is high, at the fast preparation method of charcoal rate.
A kind of piperazine modified lignin resin/aluminium hydroxide dual cladding red phosphorus combustion inhibitor, flame retardant mechanism includes red phosphorus original powder
The shell material of core material and inorganic material aluminium hydroxide and piperazine modified lignin polymer (L-P) composition of composition, by each component
Between mass percent meter, 15 %-35 % of core material, 65 %-85 % of shell material in fire retardant.Wherein shell material is using lignin as just
Beginning raw material, then passes through methylolation and piperazine moieties are grafted on lignin molecule by Mannich reaction, finally using reversed
The process of co-precipitation introduces aluminium hydroxide molecule, forms a kind of microencapsulated powder oil that multicomponent synergistic is fire-retardant.
Wherein the structure of L-P is as follows:
Flame retardant compositions are as follows:
L-P 45-65 wt%；
Aluminium hydroxide 10-30 wt%；
Red phosphorus 10-30 wt%；
Dispersing agent 0.1-0.3 wt%.
Its prepare the following steps are included:
(1) lignin and aqueous slkali are placed in three neck round bottom flask, are stirred under the conditions of 60-90 DEG C, it is sufficiently molten to lignin
Aldehyde solution is added when stablizing in solution and temperature, is stirred to react 0.5-2.0 h and obtains lignin hydroxylation product；
(2) to piperazine is added in step (1), temperature is maintained at 60-90 DEG C, continues to be stirred to react 1-3 h obtaining piperazine innovation wood
Quality performed polymer；
(3) dispersing agent is added into step (2) and red phosphorus, temperature is maintained at 60-90 DEG C, continue to be stirred to react 0.5-1.0 h,
Red phosphorus is set to be uniformly dispersed；Aluminium salt temperature is then added and is maintained at 60-90 DEG C, continues to be stirred to react 0.5-1.0 h.Stand 12 h
More than, filtration washing, 70-80 DEG C of drying to constant weight pulverizes and sieves to get double to the piperazine modified lignin resin/aluminium hydroxide
Weight Wrapped up Phosphorus Fire Retardant.
Alkali described in step (1) is one or more of sodium hydroxide, potassium hydroxide, barium hydroxide, in aqueous slkali
OH-Mass concentration be 2-10wt%.
Lignin described in step (1) can be in enzymolysis xylogen, alkali lignin, organosolv lignin, lignosulfonates
One or more, lignin dosage be 20-100 g/mol OH-。
Aldehyde described in step (1) is one or more of formaldehyde, acetaldehyde, butyraldehyde, and the dosage of aldehyde is 0.1-0.2
Mol/10 g lignin；The reaction temperature is 60-90 DEG C, and stirring rate is 400-500 r/min, and the reaction time is
0.5-2.0 h。
Piperazine described in step (2) includes one of Piperazine anhydrous or anthalazine or a variety of, and the dosage of piperazine is
0.05-0.1 molg/10 g lignin；The reaction temperature is 60-90 DEG C, and stirring rate is 400-500 r/min, instead
It is 1.0-3.0h between seasonable.
Dispersing agent described in step (3) includes neopelex, calgon, lauryl sodium sulfate, OP-
One or more of 10, the dosage of dispersing agent is 0.005-0.015 g/g red phosphorus.The red phosphorus includes that purity is 95
The wt% red phosphorus raw material of wt% ~ 100, the dosage of red phosphorus are 6-15 g/10g lignin.
Aluminium salt described in step (3) includes one of aluminum nitrate, aluminium chloride, aluminium acetate, aluminum sulfate, aluminium citrate or more
Kind, the dosage of aluminium salt is 0.33 mol/mol OH-。
Piperazine modified lignin resin/application of the aluminium hydroxide dual cladding red phosphorus combustion inhibitor in EVA as described above.
Remarkable advantage of the invention is:
Primary raw material lignin is grafted to form three-dimensional structure by the present invention by Mannich reaction with piperazine moieties, by reversed
Coprecipitation process introduces aluminium hydroxide molecule, red phosphorus is wrapped up, a kind of obtained microencapsulated powder oil haveing excellent performance is fire-retardant
Agent.Using the yield of piperazine modified lignin resin made from the method for the invention and aluminium hydroxide dual cladding red phosphorus up to 90 %
More than, fire retardant partial size is smaller, good stability of the dimension, is uniformly dispersed when using in EVA, can be effectively improved fire retardant and matrix
The compatibility of storeroom, flame retardant rating is up to V-0 grades of UL94 when additive amount is 40 %.In addition, fire retardant and polymer melting are total
It is generated when mixed without dust, improves the safety of process.
Detailed description of the invention
Fig. 1 is this patent implementation flow chart；
Fig. 2 is the SEM figure of red phosphorus (a) used in embodiment 1 and prepared fire retardant (b)；
Fig. 3 is the FT-IR figure of lignin used in embodiment 1 and prepared fire retardant；
Fig. 4 is the SEM figure of layer of charcoal after the burning of batten prepared by Application Example 1；
Fig. 5 is the SEM figure of layer of charcoal after the burning of batten prepared by Application Example 2；
Fig. 6 is the SEM figure of layer of charcoal after the burning of batten prepared by Application Example 3.
Specific embodiment
In order to make content of the present invention easily facilitate understanding, With reference to embodiment to of the present invention
Technical solution is described further, but the present invention is not limited only to this.
Embodiment 1:
8 g sodium hydroxides are weighed in beaker, the sodium hydroxide solution that deionized water compound concentration is 4 wt% are added, by 20 g
Enzymolysis xylogen adds in sodium hydroxide solution, and heating stirring is completely dissolved in lignin in lye, is subsequently moved within and is equipped with
In 500 mL three neck round bottom flask of condenser pipe and magneton.Stablize to temperature at 90 DEG C, the 40 of 24 mL are added into solution
Wt% formalin, constant temperature are stirred to react 1 h and obtain lignin hydroxylation product.It is anhydrous that 8.6 g are rapidly joined into reaction solution
Piperazine continues magnetic agitation and reacts 2 h, obtains piperazine modified lignin resin performed polymer.Add into piperazine modified lignin resin performed polymer
Enter the neopelex and 16 g red phosphorus of 160 mg, 90 DEG C are continued to be dispersed with stirring 30 min, then slowly into solution
25.0 g, nine water aluminum nitrate is added, obtains brown precipitate, continues 90 DEG C and is stirred to react 30 min.It is old that gained suspension will be reacted
After changing 12 h, filtering is washed with deionized, and is dried in 70 DEG C of baking ovens to constant weight, is obtained piperazine modified lignin resin/hydroxide
Aluminium dual cladding red phosphorus combustion inhibitor.Product is mechanically pulverized, 200 meshes is crossed, is sealed.
Embodiment 2:
11.2 g potassium hydroxide are weighed in beaker, deionized water is added and makes the potassium hydroxide solution that concentration is 4 wt%, it will
24 g alkali lignins add in potassium hydroxide solution, and heating stirring is completely dissolved in lignin in lye, is subsequently moved within dress
In the 500 mL three neck round bottom flask for having condenser pipe and magneton.Stablize to temperature at 90 DEG C, is added 24 mL's into solution
40wt % acetaldehyde solution, constant temperature are stirred to react 1 h and obtain lignin hydroxylation product.8.6 g are rapidly joined into reaction solution
Piperazine anhydrous continues magnetic agitation and reacts 2 h, obtains piperazine modified lignin resin performed polymer.To piperazine modified lignin resin performed polymer
The middle lauryl sodium sulfate and 16 g red phosphorus that 160 mg are added, 90 DEG C are continued to be dispersed with stirring 30 min, are then delayed into solution
It is slow that 8.9 g aluminium chloride are added, brown precipitate is obtained, continues 90 DEG C and is stirred to react 30 min.It will reaction gained suspension ageing
After 12 h, filtering is washed with deionized, and is dried in 70 DEG C of baking ovens to constant weight, is obtained piperazine modified lignin resin/aluminium hydroxide
Dual cladding red phosphorus combustion inhibitor.Product is mechanically pulverized, 200 meshes is crossed, is sealed.
Embodiment 3:
8 g sodium hydroxides are weighed in beaker, the sodium hydroxide solution that deionized water compound concentration is 4 wt% are added, by 24 g
Enzymolysis xylogen adds in sodium hydroxide solution, and heating stirring is completely dissolved in lignin in lye, is subsequently moved within and is equipped with
In 500 mL three neck round bottom flask of condenser pipe and magneton.Stablize to temperature at 90 DEG C, 40 % of 24 mL are added into solution
Formalin, constant temperature are stirred to react 1 h and obtain lignin hydroxylation product.19.4 g, six water piperazine is rapidly joined into reaction solution
Piperazine continues magnetic agitation and reacts 2 h, obtains piperazine modified lignin resin performed polymer.It is added into piperazine modified lignin resin performed polymer
The calgon of 200 mg and 20 g red phosphorus, 90 DEG C are continued to be dispersed with stirring 30 min, and 13.6 are then slowly added into solution
G aluminium acetate obtains brown precipitate, continues 90 DEG C and is stirred to react 30 min.After 12 h of gained suspension ageing will be reacted, mistake
Filter, is washed with deionized, and dries in 70 DEG C of baking ovens to constant weight, it is red to obtain piperazine modified lignin resin/aluminium hydroxide dual cladding
Phosphorus fire retardant.Product is mechanically pulverized, 200 meshes is crossed, is sealed.
Application Example 1:
Piperazine modified lignin resin/30 parts of aluminium hydroxide dual cladding red phosphorus combustion inhibitor (parts by weight) that embodiment 1 obtains is weighed,
It is stirred and evenly mixed with 70 parts of EVA resin (parts by weight), dry 24 h at 80 DEG C.Two kinds of raw mixtures are added to miniature
In double screw extruder, wherein processing temperature is 150 DEG C, 60 r/min of twin-screw revolving speed, recycles 5 min；In miniature injection machine
Middle injection moulding, wherein 30 DEG C of mold temperature, 8 s of pressure maintaining take out sample to get the EVA resin after flame-retardant modified.Sample rule
Lattice are the mm × 3.2 of 130 mm × 10 mm, and vertical burn test grade is up to V-0 grades of UL94.Fire-retardant batten is in Muffle furnace
Carbon yield is 22.13 % after sufficiently carbonizing at 500 DEG C.Squeezing out melt index of the pellet under 150 DEG C, 2.16 Kg load is
Melt index of the pure EVA of 3.23 g/10min(under 150 DEG C, 2.16 Kg load is 4.58 g/10min).
Application Example 2:
Piperazine modified lignin resin/30 parts of aluminium hydroxide dual cladding red phosphorus combustion inhibitor that embodiment 2 obtains is weighed, with EVA resin
70 parts stir and evenly mix, dry 24 h at 80 DEG C.Two kinds of raw mixtures are added in Minitype twin-screw extrusion machine, wherein
Processing temperature is 150 DEG C, 60 r/min of twin-screw revolving speed, recycles 5 min；It is injection moulded in miniature injection machine, wherein mold
30 DEG C of temperature, 8 s of pressure maintaining, sample is taken out to get the EVA resin after flame-retardant modified.Sample specification be the mm of 130 mm × 10 ×
3.2 mm, vertical burn test grade is up to V-0 grades of UL94.Fire-retardant batten is residual after sufficiently carbonizing at 500 DEG C in Muffle furnace
Charcoal rate is 22.53 %.Squeezing out melt index of the pellet under 150 DEG C, 2.16 Kg load is 3.33 g/10min.
Application Example 3:
Piperazine modified lignin resin/30 parts of aluminium hydroxide dual cladding red phosphorus combustion inhibitor that embodiment 3 obtains is weighed, with EVA resin
70 parts stir and evenly mix, dry 24 h at 80 DEG C.Two kinds of raw mixtures are added in Minitype twin-screw extrusion machine, wherein
Processing temperature is 150 DEG C, 60 r/min of twin-screw revolving speed, recycles 5 min；It is injection moulded in miniature injection machine, wherein mold
30 DEG C of temperature, 8 s of pressure maintaining, sample is taken out to get the EVA resin after flame-retardant modified.Sample specification be the mm of 130 mm × 10 ×
3.2 mm, vertical burn test grade is up to V-0 grades of UL94.Fire-retardant batten is residual after sufficiently carbonizing at 500 DEG C in Muffle furnace
Charcoal rate is 22.56 %.Squeezing out melt index of the pellet under 150 DEG C, 2.16 Kg load is 3.38 g/10min.
Compare Application Example:
30 parts of commercially available microencapsulated powder oil fire retardant is weighed, is stirred and evenly mixed with 70 parts of EVA resin, dry 24 h at 80 DEG C.It will
Two kinds of raw mixtures are added in Minitype twin-screw extrusion machine, and wherein processing temperature is 150 DEG C, 60 r/ of twin-screw revolving speed
Min recycles 5 min；Be injection moulded in miniature injection machine, wherein 30 DEG C of mold temperature, 6 s of pressure maintaining, take out sample to get
EVA resin after flame-retardant modified.Sample specification is the mm × 3.2 of 130 mm × 10 mm, and vertical burn test grade is up to UL94
V-2 grades.Carbon yield is 13.56 % after fire-retardant batten sufficiently carbonizes at 500 DEG C in Muffle furnace.Squeeze out pellet 150 DEG C,
Melt index under 2.16 Kg load is 2.98 g/10min.
Fig. 2 is the SEM figure of red phosphorus (a) used in embodiment 1 and prepared fire retardant (b).It can be clear by picture comparison
Ground finds out that red phosphorus is the smooth elongated irregular block in surface, it is little to be wrapped by rear change in shape, but volume becomes larger, surface is thick
It is rough, there is apparent clad, shows that red phosphorus is tightly wrapped up.
Fig. 3 is the FT-IR figure of lignin used in embodiment 1 and prepared fire retardant, and A curve is used in embodiment 1 in figure
The FT-IR of lignin schemes, and B curve is the FT-IR figure of fire retardant prepared by embodiment 1.Compare A, B curve it is found that fire retardant compared with
Lignin basic structure is remained well.But in 3160cm-1Nearby there is wide and strong absorption peak, belongs to the N-H of piperazine
Stretching vibration absworption peak, and in 536 cm-1Nearby there is a wide Al-O absorption peak.In conjunction with Fig. 2, show piperazine innovation wood
Quality and aluminium hydroxide dual cladding are on red phosphorus surface.
Fig. 4-6 is the SEM figure of layer of charcoal after the burning of batten prepared by Application Example 1-3 respectively.As seen from the figure, gained charcoal
Layer is comparatively dense, shows that sample has preferable flame retardant property, consistent with the UL-94 flame retardant rating measured.
In order to make content of the present invention easily facilitate understanding, above in conjunction with specific embodiment to of the present invention
Technical solution does the explanation further clarified, but the present invention is not limited only to this, what all Spirit Essences according to the present invention were done
Equivalence changes or modification are all the ranges for belonging to the present invention and being protected.
Claims (9)
1. a kind of piperazine modified lignin resin/aluminium hydroxide dual cladding red phosphorus combustion inhibitor, it is characterised in that: flame retardant mechanism includes
The core material and inorganic material aluminium hydroxide of red phosphorus original powder composition and the shell material of piperazine modified lignin polymer L-P composition, resistance
Fire agent component are as follows:
L-P 45-65 wt%；
Aluminium hydroxide 10-30 wt%；
Red phosphorus 10-30 wt%；
Dispersing agent 0.1-0.3 wt%.
2. piperazine modified lignin resin/aluminium hydroxide dual cladding red phosphorus combustion inhibitor preparation method according to claim 1,
It is characterized in that: the following steps are included:
(1) lignin and aqueous slkali are placed in three neck round bottom flask, are stirred under the conditions of 60-90 DEG C, it is sufficiently molten to lignin
Aldehyde solution is added when stablizing in solution and temperature, is stirred to react 0.5-2.0 h and obtains lignin hydroxylation product；
(2) to piperazine is added in step (1), temperature is maintained at 60-90 DEG C, continues to be stirred to react 1-3 h obtaining piperazine innovation wood
Quality performed polymer；
(3) dispersing agent is added into step (2) and red phosphorus, temperature is maintained at 60-90 DEG C, continue to be stirred to react 0.5-1.0 h,
Red phosphorus is set to be uniformly dispersed；Aluminium salt temperature is then added and is maintained at 60-90 DEG C, continues to be stirred to react 0.5-1.0 h, stands 12 h
More than, filtration washing, 70-80 DEG C of drying to constant weight pulverizes and sieves dual to get the piperazine modified lignin resin/aluminium hydroxide
Wrapped up Phosphorus Fire Retardant.
3. preparation method according to claim 2, it is characterised in that: alkali described in step (1) is sodium hydroxide, hydroxide
One or more of potassium, barium hydroxide, OH in aqueous slkali-Mass concentration be 2-10wt%.
4. preparation method according to claim 2, it is characterised in that: lignin described in step (1) be enzymolysis xylogen,
One or more of alkali lignin, organosolv lignin, lignosulfonates, lignin dosage are 20-100 g/mol
OH-。
5. preparation method according to claim 2, it is characterised in that: aldehyde described in step (1) is formaldehyde, acetaldehyde, butyraldehyde
One or more of, the dosage of aldehyde is 0.1-0.2 mol/10 g lignin；Stirring rate is 400-500 r/min.
6. preparation method according to claim 2, it is characterised in that: piperazine described in step (2) include Piperazine anhydrous or
One of anthalazine is a variety of, and the dosage of piperazine is 0.05-0.1 molg/10 g lignin；Stirring rate is 400-500
r/min。
7. preparation method according to claim 2, it is characterised in that: dispersing agent described in step (3) includes dodecyl
One or more of benzene sulfonic acid sodium salt, calgon, lauryl sodium sulfate, OP-10, the dosage of dispersing agent are 0.005-
0.015 g/g red phosphorus, the red phosphorus include that purity is the wt% of 95 wt% ~ 100 red phosphorus raw material, and the dosage of red phosphorus is 6-15 g/
10g lignin.
8. preparation method according to claim 2, it is characterised in that: aluminium salt described in step (3) includes aluminum nitrate, chlorination
One of aluminium, aluminium acetate, aluminum sulfate, aluminium citrate are a variety of, and the dosage of aluminium salt is 0.33 mol/mol OH-；Stirring rate
For 400-500 r/min.
9. a kind of piperazine modified lignin resin as described in claim 1/aluminium hydroxide dual cladding red phosphorus combustion inhibitor is in EVA resin
Middle application.
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| CN108997615B (en) | 2020-04-10 |
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