CN106589800A - Method for enhancing toughness of phenolic resin foam board by using reclaimed PET (polyethylene terephthalate) material - Google Patents
Method for enhancing toughness of phenolic resin foam board by using reclaimed PET (polyethylene terephthalate) material Download PDFInfo
- Publication number
- CN106589800A CN106589800A CN201611206365.5A CN201611206365A CN106589800A CN 106589800 A CN106589800 A CN 106589800A CN 201611206365 A CN201611206365 A CN 201611206365A CN 106589800 A CN106589800 A CN 106589800A
- Authority
- CN
- China
- Prior art keywords
- phenolic resin
- reclaimed materials
- phenol
- pet
- toughness
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/141—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08J2361/14—Modified phenol-aldehyde condensates
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
Abstract
The invention discloses a method for enhancing the toughness of a phenolic resin foam board by using reclaimed PET (polyethylene terephthalate) material, which relates to phenolic resin. The provided method for enhancing the toughness of a phenolic resin foam board by using reclaimed PET (polyethylene terephthalate) material has the advantages of low cost, high toughness, low free phenol and formaldehyde contents and low density and pulverization. Expandable phenolic resin prepolymer is prepared with phenol and paraformaldehyde as materials; impurity-removed reclaimed PET material is dissolved in a quaternary ammonium salt and phenol deep-eutectic solvent, so that a phenol solution of the reclaimed PET material is obtained, the expandable phenolic resin prepolymer, a foaming agent, a reinforcing agent and a curing agent are then added, and after foaming and curing, the phenolic resin foam board is obtained.
Description
Technical field
The present invention relates to phenolic resin, is related to a kind of method that use PET reclaimed materials strengthen phenolic resin toughness.
Background technology
PET (polyethylene terephthalate) kind polyesters being widely used in human being's production and life, can be used as drink
Packing container, fiber-grade polyester, mylar and the engineering plastics such as material food etc..China's soft drink yield is with the year more than 20%
Rate of increase is incremented by, and its wrapping PET bottle demand is also increased with 18% speed.Can not keep away in PET polyester production process
Waste product and leftover pieces etc. can be produced with exempting from；Additionally, the garbage produced after PET polyester uses, such as with waste mineral water bottle number
Amount is sharply increased, and a considerable number of PET reclaimed materials are obtained from these waste products, leftover pieces and garbage.The natural degradation of PET
Speed is slow, the degraded for having 30～40 years only 50% in humidity is the environment that 45%～100%, temperature is 20 DEG C, seriously
Pollute environment and cause greatly waste.In the face of substantial amounts of PET reclaimed materials, how to realize that it is recycled and become one urgently
The problem of solution.
Phenolic resin foamed board material is mainly used in architecture exterior wall insulating materials, and compared with other insulation materials, it prepares letter
It is single, good flame retardation effect；But the poor toughness of phenolic foam sheet, fragility are big, sheet material not impact resistance, easily cracking, efflorescence.Preparing
During, there are substantial amounts of free phenol and free aldehyde to be fully cured and remain in the product, the performance and human body to product
Harm is big.These shortcomings of phenolic foam sheet limit its application in exterior-wall heat insulation market, therefore should in the urgent need to improving
The toughness of material, reduces the content of free phenol and aldehyde.Furthermore, present phenolic foam sheet manufacturer is numerous, and dog-eat-dog has
Effect ground reduces production cost becomes the key for improving product competitiveness in the market.
Chinese patent CN104193933A discloses a kind of preparation method of the phenolic resin of toughness reinforcing, including：By paraformaldehyde,
Phenol and 1- methyl -4- [(dimethylamino) methyl] -2- [(3,4- difluorophenyl) sulfidomethyl] the bromo- 1H- indole of -5- hydroxyl -6- -
3- carboxylate hydrochlorides, add there-necked flask, are then respectively adding N-N dimethylethanolamines and glycerol, and there-necked flask is put
In oil bath pan, condensed water, agitator are opened, temperature rises to 65 DEG C, and stirring is melted completely up to paraformaldehyde, then by temperature
Rise to 98 DEG C, keep 2h, with psychrolusia mixture is cooled to into 60 DEG C immediately afterwards, add carbamide, remove free in resin
Phenol and free formaldehyde, keep duration 30min, are subsequently cooled to room temperature, are subsequently adding pentane, silicone oil, the phenol of 65 weight %
Sulfonic acid aqueous solution and Tween 80, then in high speed agitator under conditions of 500rpm stir 3 hours, obtain final product.The invention
The phenolic resin of toughness reinforcing obtained in method has enhanced mechanical property, has broad prospects in commercial Application.
Chinese patent CN104327229A discloses a kind of toughening modifying phenolic resin, and it is prepared by following methods：(1) prepare
Aromatic Polyester Polyols；(2) toughening modifying phenolic resin is prepared：Reactor is added after first phenol is dissolved, then is added stage by stage
Formalin, base catalyst, adjust pH=9, add triphenyl phosphate or triphenyl phosphite or triphenyl borate certain
At a temperature of make phenolic resin prepolymer, add Aromatic Polyester Polyols, react to obtain toughening modifying phenolic resin.The invention is adopted
With Aromatic Polyester Polyols as intrinsic toughening agent phenol-formaldehyde resin modified, the phenol formaldehyde foam toughness of preparation is obviously improved, scaling-off little, pressure
Contracting intensity is high, and comprehensive mechanical property is good.
The content of the invention
Present invention aims to the drawbacks described above that prior art is present, there is provided with low cost, toughness is high, free phenol
The method that the low a kind of use PET reclaimed materials of, density low with aldehyde and efflorescence strengthen phenolic resin foamed board toughness.
The present invention is comprised the following steps：
1) expandable phenolic resin performed polymer is prepared for raw material by phenol and paraformaldehyde；
2) in the PET reclaimed materials after impurity and purification being dissolved in into quaternary ammonium salt and phenol eutectic solvent, the benzene of PET reclaimed materials is obtained
Phenol solution, adds step 1) the expandable phenolic resin performed polymer, foaming agent, reinforcing agent and the firming agent that obtain, foamed solidification
After obtain final product phenolic resin foamed board.
In step 2) in, the phenol solution of the PET reclaimed materials, expandable phenolic resin performed polymer, foaming agent, reinforcement
Agent, the mass ratio of firming agent can be：(10～30) ︰ (70～90) ︰ (2～10) ︰ (10～40)：(10～20)；The PET is reclaimed
Material can adopt the recovery of garbage after the waste product and leftover pieces, and PET polyester uses produced in PET polyester production process
Material；The quaternary ammonium salt can be with the preparation method of phenol eutectic solvent：Quaternary ammonium salt and phenol heated and stirred are formed into eutectic
Solvent, wherein quaternary ammonium salt are 75%～125% with the mass percent of phenol；The preparation of the phenol solution of the PET reclaimed materials
Method can be：By PET reclaimed materials, tablet of the size diameter less than 1cm is sliced into Jing after remove impurity is processed, is added into quaternary ammonium
In salt and phenol eutectic solvent, the phenol solution of PET reclaimed materials is obtained final product after heated and stirred；The PET reclaimed materials and quaternary ammonium salt
Can be for (10～30) ︰ (50～120), the temperature of the heating can be 50～120 DEG C with the mass ratio of phenol eutectic solvent.
The foaming agent may be selected from least one in pentane, normal hexane, petroleum ether etc.；Described reinforcing agent may be selected from
Al(OH)3、Mg(OH)2At least one in；The firming agent may be selected from p-methyl benzenesulfonic acid, xylene monosulfonic acid, to oxybenzene sulphur
At least one in acid, sulphuric acid, phosphoric acid etc..
All raw materials in the present invention can be buied or be subsequently obtained in market at home.
In the present invention, the mechanism of PET polyester-modified phenolic resins is：PET (polyethylene terephthalate) is by benzene
Dioctyl phthalate and two kinds of monomer polycondensations of ethylene glycol and obtain, the rigid radicals such as phenyl ring had both been contained in its molecule segment, ethylene glycol is contained again
Etc. flexible composition.In a heated condition, raw material phenol is the fine solvent of PET reclaimed materials, therefore PET and phenolic resin system
The compatibility is fine, without the need for carrying out special handling to it.After being dissolved in phenol, molecule segment depolymerization, terminal hydroxy group has very high
Reactivity, can with the methylol in expandability phenolic aldehyde performed polymer occur grafting or block copolymerization and reaction, so as to will rigidity
Benzene radicals with flexibility glycol group be introduced in the structure of phenolic resin, fundamentally change the rigidity of phenolic resin
Molecular structure, so as to reduce the fragility of phenol formaldehyde foam, improves its toughness.Additionally, containing the benzene that rigidity is strong in the monomer of PET
Ring, can equally play the fire-retardant effect similar with phenolic resin, and compared with simple fatty long-chain plasticizing phenol formaldehyde is introduced, the former
The fire resistance of product after toughness reinforcing can be ensured will not be decreased obviously, better.
The eutectic solvent degraded PET reclaimed materials that the present invention is formed using quaternary ammonium salt and phenol, it is poly- using resulting PET
The catabolites such as the oligomer and monomer of ester, in adding the phenolic resin performed polymer prepared for raw material by phenol and paraformaldehyde,
Cellular insulant is produced in the presence of foaming agent and firming agent, to increase the toughness and intensity of phenolic resin foamed board material.
The production method of a kind of inexpensive toughening metlbond foam sheet material for being provided, PET reclaimed materials wide material sources are cheap, reduce
Industrial cost, reduces pollution of the waste PET polyester to environment, also improves the intensity and toughness of phenolic aldehyde heat preserving sheet material, drops
The fragility of low sheet material, while meeting the needs of skin construction.
One of the advantages of the present invention is, in a heated condition, raw material phenol is the fine solvent of PET reclaimed materials, therefore PET
The compatibility with phenolic resin system is fine, and terminal hydroxy group present in PET has very high reactivity, can be pre- with phenolic aldehyde
The hydroxyl reaction dehydration of polymers obtains polymer, the toughened copolymer thing modified so as to obtain chemical doping.Additionally, the monomer of PET
In containing the strong phenyl ring of rigidity, can equally play the fire-retardant effect similar with phenolic resin, introduce fat long-chain compared with simple
Plasticizing phenol formaldehyde, the former can ensure that the fire resistance of product after toughness reinforcing will not be decreased obviously, better.
The two of advantages of the present invention are, using abundance and cheap PET reclaimed materials are to phenolic resin foamed board
Material carries out toughness reinforcing, can alleviate increasing pet waste reserves, strengthens the toughness of phenolic foam sheet product, and reduces being somebody's turn to do
The production cost of class product.
Specific embodiment
Below in conjunction with specific embodiment, the invention will be further described, but not thereby limiting the invention.
Embodiment 1
Step 1：Weigh the NaOH aqueous solutions that 500 parts of phenol, 300 parts of paraformaldehydes, 36 parts of mass fractions are 20%.By benzene
In phenol input reactor, it is warming up to 70 DEG C and melts, while stirring, add paraformaldehyde, keeps 30min；Add sodium hydroxide
Solution, stirs.Raise temperature in reactor and, to 100 DEG C, keep temperature 30min, expandable phenolic resin pre-polymerization is obtained
Body.
Step 2：By 50 parts of choline chlorides and 50 parts of phenol are weighed, mix after 25 DEG C of heating, obtain eutectic solvent.Will
Standby PET reclaimed materials are cut into section of the diameter less than 1cm, in adding above-mentioned eutectic solvent, the two quality point after cleaning
Several ratios are：PET is 20 parts, and eutectic solvent is 100 parts, is warming up to 50 DEG C of stirring 30min so that added PET material are complete
Portion dissolves, and obtains the catabolites such as the oligomer and monomer of PET polyester (hereinafter referred to as PET degraded solutions).
Step 1 gained expandable phenolic resin performed polymer is added in another reactor, 100 DEG C are warming up to, step 2 is added
The PET degraded solutions of gained, and add reinforcing agent Al (OH)3, foaming agent pentane and p-methyl benzenesulfonic acid and sulphuric acid mixing
Acid as curing agent, mixing and stirring injects default board mould.Expandable phenolic resin performed polymer, PET degraded solutions, benefit
Strong agent Al (OH)3, foaming agent pentane, the mass ratio of the mixing acid as curing agent of p-methyl benzenesulfonic acid and sulphuric acid be the ︰ of 70 ︰, 10 ︰, 10 ︰ 4
10.50 ± 2 DEG C of 5～20min of mold temperature are kept, 70 ± 2 DEG C of 10～30min of maintenance are then heated to, then is cooled to 50 ± 2 DEG C
5～20min is maintained, 35 ± 2 DEG C are finally cooled to, mould is removed, phenolic resin foamed board, i.e. toughening modifying phenolic resin is obtained final product
Cystosepiment.
After testing, its pore size distribution is uniform for gained toughening modifying phenolic resin foamed board, and rate of closed hole is high, and average pore size is 55～
90μm。
Embodiment 2
Step 1：Weigh the NaOH aqueous solutions that 500 parts of phenol, 300 parts of paraformaldehydes, 36 parts of mass fractions are 20%.By institute
In standby phenol input reactor, it is warming up to 70 DEG C and melts, while stirring, add paraformaldehyde, keeps 30min；Add
Above-mentioned sodium hydroxide solution, stirs.Raise temperature in reactor and, to 100 DEG C, keep temperature 30min, expandability is obtained
Phenolic resin performed polymer.
Step 2：50 parts of tetramethyl ammonium chlorides and 50 parts of phenol are weighed, is mixed after 25 DEG C of heating, obtain eutectic solvent.
Standby PET reclaimed materials are cut into section of the diameter less than 1cm, in adding above-mentioned eutectic solvent, the two quality after cleaning
The ratio of fraction is：PET is 20 parts, and eutectic solvent is 100 parts, is warming up to 50 DEG C of stirring 30min so that added PET material
All dissolving, obtains PET degraded solutions.
Step 1 gained phenolic resin performed polymer is added in another reactor, 100 DEG C are warming up to, step 2 gained is added
PET degradation solutions, and add reinforcing agent Al (OH)3, foaming agent n-hexane, and p-methyl benzenesulfonic acid and sulphuric acid mixed acid solidification
Agent, mixing and stirring injects default board mould.Phenolic resin performed polymer, PET degraded solutions, reinforcing agent Al (OH)3、
The mass fraction ratio of the mixing acid as curing agent of foaming agent pentane, p-methyl benzenesulfonic acid and sulphuric acid is the ︰ 10 of 70 ︰, 10 ︰, 10 ︰ 4.
50 ± 2 DEG C of 5～20min of mold temperature are kept, 70 ± 2 DEG C of 10～30min of maintenance are then heated to, then is cooled to 50
± 2 DEG C of 5～20min of maintenance, are then cooled to 35 ± 2 DEG C, remove mould, obtain final product the PET reclaimed materials toughening modifying phenol of the present invention
Aldehyde foam board.
Embodiment 3
Step 1：Weigh the NaOH aqueous solutions that 500 parts of phenol, 300 parts of paraformaldehydes and 36 parts of mass fractions are 20%.Will
In standby phenol input reactor, be warming up to 70 DEG C and melt, while stirring, add paraformaldehyde, keep 30min；Plus
Enter above-mentioned sodium hydroxide solution, stir.Raise temperature in reactor and, to 100 DEG C, keep temperature 30min, being obtained to send out
Property phenolic resin performed polymer.
Step 2：50 parts of tetraethylammonium chlorides and 50 parts of phenol are weighed, is mixed after 25 DEG C of heating, obtain eutectic solvent.
Standby PET reclaimed materials are cut into section of the diameter less than 1cm, in adding above-mentioned eutectic solvent, the two quality after cleaning
The ratio of fraction is：PET is 20 parts, and eutectic solvent is 100 parts, is warming up to 50 DEG C of stirring 30min so that added PET material
All dissolving, obtains PET degraded solutions.
Step 1 gained phenolic resin performed polymer is added in another reactor, 100 DEG C are warming up to, step 2 gained is added
PET degraded solutions, and add reinforcing agent Al (OH)3, foaming agent pentane, and p-methyl benzenesulfonic acid and sulphuric acid mixed acid solidification
Agent, mixing and stirring injects default board mould.Phenolic resin performed polymer, PET degraded solutions, reinforcing agent Al (OH)3、
The mass fraction ratio of the mixing acid as curing agent of foaming agent pentane, p-methyl benzenesulfonic acid and sulphuric acid is the ︰ 10 of 70 ︰, 10 ︰, 10 ︰ 4.
50 ± 2 DEG C of 5～20min of mold temperature are kept, 70 ± 2 DEG C of 10～30min of maintenance are then heated to, then is cooled to 50
± 2 DEG C of 5～20min of maintenance, are then cooled to 35 ± 2 DEG C, remove mould, obtain final product the PET reclaimed materials toughening modifying phenol of the present invention
Aldehyde foam board.
Embodiment 4
Step 1：Weigh the NaOH aqueous solutions that 500 parts of phenol, 300 parts of paraformaldehydes, 36 parts of mass fractions are 20%.By institute
In standby phenol input reactor, it is warming up to 70 DEG C and melts, while stirring, add paraformaldehyde, keeps 30min；Add
Above-mentioned sodium hydroxide solution, stirs.Raise temperature in reactor and, to 100 DEG C, keep temperature 30min, expandability is obtained
Phenolic resin performed polymer.
Step 2：50 parts of tetrabutyl ammonium bromide are weighed, 50 parts of phenol mix after 25 DEG C of heating, obtain eutectic solvent.
Standby PET reclaimed materials are cut into section of the diameter less than 1cm, in adding above-mentioned eutectic solvent, the two quality after cleaning
The ratio of fraction is：PET is 20 parts, and eutectic solvent is 100 parts, is warming up to 50 DEG C of stirring 30min so that added PET material
All dissolving, obtains PET degraded solutions.
Step 1 gained phenolic resin performed polymer is added in another reactor, 100 DEG C are warming up to, step 2 gained is added
PET degraded solutions, and add reinforcing agent Al (OH)3, foaming agent petroleum ether, and p-methyl benzenesulfonic acid and sulphuric acid mixed acid solidification
Agent, mixing and stirring injects default board mould.Phenolic resin performed polymer, PET degraded solutions, reinforcing agent Al (OH)3、
The mass fraction ratio of the mixing acid as curing agent of foaming agent pentane, p-methyl benzenesulfonic acid and sulphuric acid is the ︰ 10 of 70 ︰, 10 ︰, 10 ︰ 4.
50 ± 2 DEG C of 5～20min of mold temperature are kept, 70 ± 2 DEG C of 10～30min of maintenance are then heated to, then is cooled to 50
± 2 DEG C of 5～20min of maintenance, are then cooled to 35 ± 2 DEG C, remove mould, obtain final product the PET reclaimed materials toughening modifying phenol of the present invention
Aldehyde foam board.
Embodiment 5
Step 1：Weigh the KOH aqueous solutions that 500 parts of phenol, 300 parts of paraformaldehydes, 36 parts of mass fractions are 20%.By institute
In standby phenol input reactor, it is warming up to 70 DEG C and melts, while stirring, add paraformaldehyde, keeps 30min；Add
Above-mentioned potassium hydroxide solution, stirs.Raise temperature in reactor and, to 100 DEG C, keep temperature 30min, expandability is obtained
Phenolic resin performed polymer.
Step 2：50 parts of choline chlorides are weighed, 50 parts of phenol mix after 25 DEG C of heating, obtain eutectic solvent.To wash
Standby PET reclaimed materials are cut into section of the diameter less than 1cm, in adding above-mentioned eutectic solvent, the two mass fraction after net
Ratio be：PET is 20 parts, and eutectic solvent is 100 parts, is warming up to 50 DEG C of stirring 30min so that added PET material are all
Dissolving, obtains PET degraded solutions.
Step 1 gained phenolic resin performed polymer is added in another reactor, 100 DEG C are warming up to, step 2 gained is added
PET phenol solution, and add reinforcing agent Al (OH)3, foaming agent pentane, and p-methyl benzenesulfonic acid and sulphuric acid mixed acid solidification
Agent, mixing and stirring injects default board mould.Phenolic resin performed polymer, PET phenol solution, reinforcing agent Al (OH)3、
The mass fraction ratio of the mixing acid as curing agent of foaming agent pentane, p-methyl benzenesulfonic acid and sulphuric acid is the ︰ 10 of 90 ︰, 10 ︰, 10 ︰ 4.
50 ± 2 DEG C of 5～20min of mold temperature are kept, 70 ± 2 DEG C of 10～30min of maintenance are then heated to, then is cooled to 50
± 2 DEG C of 5～20min of maintenance, are then cooled to 35 ± 2 DEG C, remove mould, obtain final product the PET reclaimed materials toughening modifying phenol of the present invention
Aldehyde foam board.
Claims (10)
1. a kind of method that use PET reclaimed materials strengthen phenolic resin foamed board toughness, it is characterised in that comprise the following steps：
1) expandable phenolic resin performed polymer is prepared for raw material by phenol and paraformaldehyde；
2) in the PET reclaimed materials after impurity and purification being dissolved in into quaternary ammonium salt and phenol eutectic solvent, the phenol for obtaining PET reclaimed materials is molten
Liquid, adds step 1) the expandable phenolic resin performed polymer, foaming agent, reinforcing agent and the firming agent that obtain, after foamed solidification i.e.
Obtain phenolic resin foamed board.
2. the method that a kind of use PET reclaimed materials as claimed in claim 1 strengthen phenolic resin foamed board toughness, it is characterised in that
In step 2) in, the phenol solution of the PET reclaimed materials, expandable phenolic resin performed polymer, foaming agent, reinforcing agent, firming agent
Mass ratio be：(10～30) ︰ (70～90) ︰ (2～10) ︰ (10～40)：(10～20).
3. the method that a kind of use PET reclaimed materials as claimed in claim 1 strengthen phenolic resin foamed board toughness, it is characterised in that
In step 2) in, the PET reclaimed materials are made using the waste product and leftover pieces produced in PET polyester production process, and PET polyester
The reclaimed materials of garbage with after.
4. the method that a kind of use PET reclaimed materials as claimed in claim 1 strengthen phenolic resin foamed board toughness, it is characterised in that
In step 2) in, the quaternary ammonium salt is with the preparation method of phenol eutectic solvent：Quaternary ammonium salt and phenol heated and stirred are formed
Eutectic solvent, wherein quaternary ammonium salt are 75%～125% with the mass percent of phenol.
5. the method that a kind of use PET reclaimed materials as claimed in claim 1 strengthen phenolic resin foamed board toughness, it is characterised in that
In step 2) in, the preparation method of the phenol solution of the PET reclaimed materials is：By PET reclaimed materials, it is sliced into Jing after remove impurity is processed
Tablet of the size diameter less than 1cm, in being added into quaternary ammonium salt and phenol eutectic solvent, obtains final product PET after heated and stirred
The phenol solution of reclaimed materials.
6. the method that a kind of use PET reclaimed materials as claimed in claim 1 strengthen phenolic resin foamed board toughness, it is characterised in that
In step 2) in, the PET reclaimed materials are (10～30) ︰ (50～120) with the mass ratio of phenol eutectic solvent with quaternary ammonium salt.
7. the method that a kind of use PET reclaimed materials as claimed in claim 1 strengthen phenolic resin foamed board toughness, it is characterised in that
In step 2) in, the temperature of the heating is 50～120 DEG C.
8. the method that a kind of use PET reclaimed materials as claimed in claim 1 strengthen phenolic resin foamed board toughness, it is characterised in that
In step 2) in, at least one of the foaming agent in pentane, normal hexane, petroleum ether.
9. the method that a kind of use PET reclaimed materials as claimed in claim 1 strengthen phenolic resin foamed board toughness, it is characterised in that
In step 2) in, described reinforcing agent is selected from Al (OH)3、Mg(OH)2In at least one.
10. the method that a kind of use PET reclaimed materials as claimed in claim 1 strengthen phenolic resin foamed board toughness, its feature exists
In in step 2) in, the firming agent selected from p-methyl benzenesulfonic acid, xylene monosulfonic acid, in phenolsulfonic acid, sulphuric acid, phosphoric acid at least
It is a kind of.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611206365.5A CN106589800B (en) | 2016-12-23 | 2016-12-23 | A method of enhancing phenolic resin foamed board toughness with PET reclaimed materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611206365.5A CN106589800B (en) | 2016-12-23 | 2016-12-23 | A method of enhancing phenolic resin foamed board toughness with PET reclaimed materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106589800A true CN106589800A (en) | 2017-04-26 |
| CN106589800B CN106589800B (en) | 2018-08-07 |
Family
ID=58603423
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611206365.5A Active CN106589800B (en) | 2016-12-23 | 2016-12-23 | A method of enhancing phenolic resin foamed board toughness with PET reclaimed materials |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106589800B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112876806A (en) * | 2021-02-09 | 2021-06-01 | 常熟东南塑料有限公司 | Phenolic molding plastic toughened by PET reclaimed materials |
| CN112898728A (en) * | 2021-02-10 | 2021-06-04 | 常熟东南塑料有限公司 | Oil-resistant heat-resistant dimensionally stable phenolic moulding compound |
| CN112898727A (en) * | 2021-02-10 | 2021-06-04 | 常熟东南塑料有限公司 | Preparation method of oil-resistant heat-resistant dimensionally stable phenolic molding compound |
| CN113024990A (en) * | 2021-03-19 | 2021-06-25 | 常熟东南塑料有限公司 | High-toughness flame-retardant heat-resistant phenolic molding compound and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103641678A (en) * | 2013-12-03 | 2014-03-19 | 上海应用技术学院 | Method for degrading polyethylene glycol terephthalate (PET) |
| CN104327229A (en) * | 2014-11-06 | 2015-02-04 | 聊城大学 | Toughening modified phenolic resin and preparation method thereof |
| CN104327451A (en) * | 2014-11-06 | 2015-02-04 | 聊城大学 | Phenol formaldehyde foam by using aromatic hydrocarbon polyester polyol as toughener and preparation method thereof |
-
2016
- 2016-12-23 CN CN201611206365.5A patent/CN106589800B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103641678A (en) * | 2013-12-03 | 2014-03-19 | 上海应用技术学院 | Method for degrading polyethylene glycol terephthalate (PET) |
| CN104327229A (en) * | 2014-11-06 | 2015-02-04 | 聊城大学 | Toughening modified phenolic resin and preparation method thereof |
| CN104327451A (en) * | 2014-11-06 | 2015-02-04 | 聊城大学 | Phenol formaldehyde foam by using aromatic hydrocarbon polyester polyol as toughener and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 邓玉明等: "PET废弃物水解及醇解化学回收技术研究", 《塑料制造》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112876806A (en) * | 2021-02-09 | 2021-06-01 | 常熟东南塑料有限公司 | Phenolic molding plastic toughened by PET reclaimed materials |
| CN112898728A (en) * | 2021-02-10 | 2021-06-04 | 常熟东南塑料有限公司 | Oil-resistant heat-resistant dimensionally stable phenolic moulding compound |
| CN112898727A (en) * | 2021-02-10 | 2021-06-04 | 常熟东南塑料有限公司 | Preparation method of oil-resistant heat-resistant dimensionally stable phenolic molding compound |
| CN113024990A (en) * | 2021-03-19 | 2021-06-25 | 常熟东南塑料有限公司 | High-toughness flame-retardant heat-resistant phenolic molding compound and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106589800B (en) | 2018-08-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106589800B (en) | A method of enhancing phenolic resin foamed board toughness with PET reclaimed materials | |
| CN1249134C (en) | Polymeric composite foam | |
| CN102659992B (en) | Phenolic lignin-based modified foaming phenolic resin, foamed plastic and preparation method of phenolic lignin-based modified foaming phenolic resin | |
| CN103013038A (en) | Cardanol modified phenolic aldehyde foam and preparation method thereof | |
| JP2017206714A5 (en) | ||
| CN101381439B (en) | Thermosetting rapid curing phenolic resin and preparation method thereof | |
| CN101602275B (en) | Phenolic aldehyde foam double-metal-face chromatic steel sandwich plate and continuous production technology thereof | |
| CN103059506A (en) | Easily degradable phenolic foam and preparation method thereof | |
| CN104327451B (en) | Take Aromatic Polyester Polyols as phenol formaldehyde foam of toughner and preparation method thereof | |
| CN101985512A (en) | Physically expandable microsphere epoxy foaming material and preparation method thereof | |
| CN105086350A (en) | Toughened phenolic foamed resin with long carbon chains and preparation method thereof | |
| CN104327229B (en) | Toughening modifying resol and preparation method thereof | |
| CN103087345B (en) | Preparation method of phenolic foam | |
| CN104403263B (en) | A kind of toughness reinforcing reinforced phenolic foam board | |
| CN104403066A (en) | Graphene phenolic resin composite material and application thereof | |
| CN107974037B (en) | Application of graded lignin in preparation of phenolic foam thermal insulation material | |
| CN104387541A (en) | Toughened modified phenolic foam and preparation method thereof | |
| CN103289307A (en) | Preparation method of high energy-saving type modified environment-friendly phenolic fireproof insulation board | |
| CN108250479B (en) | Preparation method of phenolic foam with high lignin content | |
| CN102304270A (en) | Modified phenolic aldehyde foam plate and preparation process thereof | |
| CN109293941A (en) | A kind of depolymerization lignin and its preparation method and application | |
| CN104497241A (en) | Graphene phenolic resin as well as preparation method and application thereof | |
| CN104403264A (en) | Graphene phenolic resin composite material, and preparation method and application thereof | |
| CN106397698A (en) | Environment-friendly type expandable phenolic resin containing glucosyl groups and preparation method thereof | |
| CN105085972B (en) | One kind reduces acid phenolic aldehyde vacuum foam and prepares expandable phenolic resin method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210714 Address after: 251900 in Lubei high tech Development Zone, Wudi County, Binzhou City, Shandong Province Patentee after: Wudi Dexin Chemical Co.,Ltd. Address before: 831100 No.77, Beijing North Road, Changji Hui Autonomous Prefecture, Xinjiang Uygur Autonomous Region Patentee before: CHANGJI University |