CN110157145A - A kind of modified phenolic molding compound of high bending strength and preparation method thereof - Google Patents
A kind of modified phenolic molding compound of high bending strength and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to phenoplasts, disclose a kind of modified phenolic molding compound and preparation method thereof of high bending strength, when solving prior art reduction phenolaldehyde moulding compound brittleness, the problem of performances such as the tensile strength and bending modulus of phenolaldehyde moulding compound decline, a kind of modified phenolic molding compound of high bending strength, modified phenolic molding compound includes the following raw material by mass fraction: 200 parts of thermosetting phenolic resin, 2- formoxyl -3, 4-6 parts of 4- dihydropyran, 3-5 parts of polyvinyl alcohol, 0.2-4 parts of demoulding auxiliary agent, 7-12 parts of filler, 2-3.5 parts of pigment, wherein thermosetting phenolic resin is the thermosetting phenolic resin of liquid, formoxyl -3, 4- dihydropyran is first and after thermosetting phenolic resin hybrid reaction, add polyvinyl alcohol reaction, add demoulding auxiliary agent, filler, pigment into Row mixing obtains modified phenolic molding compound after carrying out refining modeling, while reducing modified phenolic molding compound brittleness, obtains the raising on rigidity and toughness properties.
Description
Technical field
The present invention relates to phenoplasts, in particular to the modified phenolic molding compound of a kind of high bending strength and its preparation side
Method.
Background technique
Phenoplasts are the thermosetting plasticses using phenolic resin as substrate, are widely used as electrically insulating material, furniture element, day
Articles, craftwork etc..Phenolaldehyde moulding compound is then one kind of phenoplasts, and by phenolic resin, filler and other additives etc. are former
Material is made.Phenolaldehyde moulding compound is identical as phenoplasts, has that biggish rigidity, heat resistance be high, property of water-fast, oil resistant and resistance to mould
Can, the problem of but it is big to there is brittleness at the same time, flexible fracture.
This in the prior art improves the formula of phenolaldehyde moulding compound.Such as Authorization Notice No. is CN102775723B
Chinese patent " a kind of high bending strength phenolaldehyde moulding compound ", include weight part ratio the following raw material composition: phenolic resin:
100 parts, thermosetting phenolic resin: 60-100 parts；Nano-rubber: 1-10 parts, curing agent: 5-30 parts, curing accelerator: 1-10
Part, release agent: 0.5-3 parts, other mineral fillers: 50-80 parts, reinforcing fiber: 60-150 parts, it has been additionally added ceramic powder filler 5-
20 parts；Phenolic resin refers to thermoplastic phenolic resin；Thermosetting phenolic resin refers to liquid or solid thermosetting phenolic tree
Rouge.
It is added in thermosetting phenolic resin using ingredients such as nano-rubber, phenolic resin and concocts brittleness, and then is improved
The bending strength of phenolaldehyde moulding compound.But it is disadvantageous in that the drawing of phenolaldehyde moulding compound while reducing phenolaldehyde moulding compound brittleness
Intensity and the decline of compression anti-deformation are stretched, causes phenolaldehyde moulding compound easily-deformable.As engineering plastics, it is intended that phenolic molding compound
Expect while having good toughness and rigidity, guarantees the intensity of phenolaldehyde moulding compound while reducing phenolaldehyde moulding compound brittleness, therefore have
It is to be modified.
Summary of the invention
In view of the deficiencies of the prior art, the present invention intends to provide a kind of modified phenolic mould of high bending strength
Plastics while modified phenolic molding compound brittleness reduces, obtain the raising on rigidity and toughness properties.
Above-mentioned technical purpose of the invention has the technical scheme that
A kind of modified phenolic molding compound of high bending strength, the modified phenolic molding compound include the following original by mass fraction
Material:
200 parts of thermosetting phenolic resin,
4-6 parts of 2- formoxyl -3,4- dihydropyran,
3-5 parts of polyvinyl alcohol,
0.2-4 parts of demoulding auxiliary agent,
7-12 parts of filler,
2-3.5 parts of pigment,
Wherein thermosetting phenolic resin is the thermosetting phenolic resin of liquid.
By using above-mentioned technical proposal, thermosetting phenolic resin is the thermosetting phenolic resin of liquid, formoxyl -3 2-,
4- dihydropyran can be reacted with the remaining phenolic hydroxyl group of thermosetting phenolic resin, be accessed in phenolic resin cross-linking system, polyvinyl alcohol
On hydroxyl and phenolic resin in hydroxyalkyl reaction forming phenolic resin cross-linking system；
The epoxy bond adjacent with carbon-carbon double bond on hydroxyl and 2- formoxyl -3,4- dihydropyran on polyvinyl alcohol, so that poly- second
Enol and 2- formoxyl -3,4- dihydropyran are combined by intermolecular interaction, generate synergistic effect, reinforce phenolic molding compound
The internal bond strength of material；
For the final phenolaldehyde moulding compound that resulting modified phenolic molding compound is more existing unmodified and brittleness is big, mechanical property is obtained
Improve, tensile strength, bending strength and impact strength are improved, and while reducing modified phenolic molding compound brittleness, are obtained
Raising in rigidity and toughness properties.
The present invention is further arranged to: the demoulding auxiliary agent is stearic acid, in calcium stearate, zinc stearate, magnesium stearate
One kind, the demolding aids mass fraction be 0.2-0.4 parts.
By using above-mentioned technical proposal, hydroxyalkyl reaction forming phenolic aldehyde tree in the hydroxyl and phenolic resin on polyvinyl alcohol
When rouge cross-linking system, the processing performance of phenolic resin is improved, mobility when phenolic resin melting is improved, reduces cooling
The adhesive of product afterwards reduces to the single release agent dosage for promoting modified phenolic molding compound, reduces auxiliary dosage, reduces and be modified
The internal remaining possibility of small molecule after phenolaldehyde moulding compound use, for being applicable in the engineering plastics required to VOC.
The present invention is further arranged to: the demoulding auxiliary agent is zinc citrate, in cocounut oil alcohol sulfuric ester zinc, zinc laurate
One kind, the demolding aids mass fraction are 2-4 parts.
By using above-mentioned technical proposal, zinc citrate, cocounut oil alcohol sulfuric ester zinc, zinc laurate are improving phenolic resin
Processing performance more can adequately mix, so that lemon while being convenient for product stripping with the thermosetting phenolic resin of liquid
Sour zinc, cocounut oil alcohol sulfuric ester zinc, the divalent zinc in zinc laurate can play the role of curing accelerator, promote modified phenolic molding
Expect the solidification rate and solidification effect in process, improve modified phenolic molding compound bending modulus, impact strength and stretches strong
Degree.
The present invention is further arranged to: the filler is modified conch meal, and the modified conch meal is by 14wt% containing NaOH
After aqueous solution soaking conch meal and the multigelation processing of urea 8wt%, washing drains to obtain.
By using above-mentioned technical proposal, modified conch meal passes through the aqueous solution soaking of NaOH 14wt% and urea 8wt%
Conch meal and multigelation processing, remove the chitin in conch meal, conch meal surface and it is internal formed a large amount of micropore and
Micro channel, while removal of the high-temperature process to conch meal surface-active hydroxyl is avoided, conch meal is improved in phenolic resin
Dispersion effect, and the binding force of conch meal and phenolic resin is improved, enhancing conch meal imitates the enhancing of modified phenolic molding compound
Fruit, and reduce modified phenolic molding compound density.
The present invention is further arranged to: the modified conch meal partial size is 1.0-2.5 μm.
By using above-mentioned technical proposal, the reinforcing effect of modified conch meal is related with the modified partial size of conch meal, modified
The partial size of conch meal is 1-2.5 μm, so that the reinforcing effect of modified conch meal reaches more excellent, while suitable partial size is accelerated to be modified
Chitin speed in conch meal preparation, and avoid partial size is too small from leading to modified conch meal filtering hardly possible, drain difficult problem.
The present invention is further arranged to: the pigment is Anthraquinones organic pigment or organic coupling agent treated inorganic powder
Last pigment.
By using above-mentioned technical proposal, pigment and phenolic resin mixing uniformity are improved, avoids pigment in phenolic aldehyde tree
Conglomeration is agglomerated in rouge, prevents phenol-formaldehyde resin modified from occurring and the discrepant color spot of ambient color.
The present invention is further arranged to: the pigment is organic coupling agent treated inorganic powder pigment, described organic
Coupling agent is titanate ester crosslinking agent.
By using above-mentioned technical proposal, pigment selects inorganic powder pigment, and organic coupling agent is titanate ester crosslinking agent
When, when phenol-formaldehyde resin modified compared with organic coupling agent is organo silane coupling agent, the plastics bending modulus of phenol-formaldehyde resin modified, impact
Intensity is improved.
In view of the deficiencies of the prior art, the present invention intends to provide a kind of modified phenolic mould of high bending strength
The preparation method of plastics improves 2- formoxyl -3,4- dihydropyran and is incorporated into the probability on the cross-linking system of phenolic resin, improves
The performance improvement of synergistic effect between 2- formoxyl -3,4- dihydropyran and polyvinyl alcohol to modified phenolic molding compound.
Above-mentioned technical purpose of the invention has the technical scheme that
A kind of preparation method of the modified phenolic molding compound of high bending strength, comprising the following steps:
S1: mass fraction weighs 200 parts of thermosetting phenolic resin of liquid, 4-6 parts of 2- formoxyl -3,4- dihydropyran, poly- second
3-5 parts of enol, 0.2-4 parts of demoulding auxiliary agent, 7-12 parts of filler, 2-3.5 parts of pigment, 10 parts of water, 10 parts of ethyl alcohol；
S2: by 4-6 parts of 2- formoxyl -3,4- dihydropyran and 200 parts of addition stirred reactors of thermosetting phenolic resin, then plus
Enter 1-2 sodium hydroxide, heating stirring, heating temperature is 95-100 DEG C, mixing time 10-30min, obtains liquid or thick shape
Mixture A；
S3: by 10 parts of 3-5 parts of polyvinyl alcohol, 10 parts of water, ethyl alcohol addition mixture A, continue to keep heating temperature to be 125 DEG C, stir
After mixing 20-30min, moisture and other small molecule by-products are sloughed in vacuum distillation after first normal pressure, obtain gelatinous mixture B；
S4: by 0.2-4 parts of demoulding auxiliary agent, 7-12 parts of filler, 2-3.5 parts of pigment and the resulting mixture B of S3 are mixed, in plastics processing mill
Upper to carry out semi-curing processing, low temperature roller temperature is 70-90 DEG C, and high temperature roller temperature is 160-180 DEG C, roll spacing 1.5-2m, when
Between 2-3min, obtain sheet products, crushing obtains a shape or powder product.
By using above-mentioned technical proposal, 2- formoxyl -3,4- dihydropyran elder generation and thermosetting phenolic resin hybrid reaction
Afterwards, polyvinyl alcohol reaction is added, demoulding auxiliary agent, filler, pigment is added and is mixed, guarantees 2- formoxyl -3,4-
The aldehyde radical of dihydropyran is first reacted with the phenolic hydroxyl group of phenolic resin, avoids hydroxyl and 2- formoxyl -3,4- bis- on polyvinyl alcohol
The aldehyde radical of hydrogen pyrans reacts and 2- formoxyl -3,4- dihydropyran is hindered to be incorporated on the cross-linking system of phenolic resin, improves 2-
Formoxyl -3,4- dihydropyran is incorporated into the probability on the cross-linking system of phenolic resin, improves 2- formoxyl -3,4- dihydropyran
The performance improvement of synergistic effect between polyvinyl alcohol to modified phenolic molding compound；
And if demoulding auxiliary agent has and promotes cured effect herein, after demolding aids and in 2- formoxyl -3,4- dihydropyran
And polyvinyl alcohol, slow down 2- formoxyl -3,4- dihydropyran and polyvinyl alcohol be mixed into during phenolic resin stickyization rate, just
It is stirred after 2- formoxyl -3,4- dihydropyran and polyvinyl alcohol are added.
In conclusion the invention has the following advantages:
1.2- formoxyl -3,4- dihydropyran and polyvinyl alcohol can access in phenolic resin cross-linking system, while on polyvinyl alcohol
Hydroxyl and 2- formoxyl -3,4- dihydropyran on the epoxy bond adjacent with carbon-carbon double bond so that polyvinyl alcohol and 2- formoxyl -
3,4- dihydropyran are combined by intermolecular interaction, are generated synergistic effect, are reinforced the internal bond strength of phenolaldehyde moulding compound；
For the final phenolaldehyde moulding compound that resulting modified phenolic molding compound is more existing unmodified and brittleness is big, mechanical property is changed
Kind, tensile strength, bending strength and impact strength are improved, and while reducing modified phenolic molding compound brittleness, are obtained rigid
Raising in property and toughness properties；
2. access phenolic resin cross-linking system on polyvinyl alcohol, the processing performance of phenolic resin is improved, improves phenolic aldehyde
Mobility when resin melting reduces the adhesive of product after cooling, can reduce and take off to single promotion modified phenolic molding compound
Mould agent dosage reduces the remaining possibility of small molecule for the engineering plastics required to VOC are applicable in；
3. can promote modified phenolic outside the effect of zinc citrate, cocounut oil alcohol sulfuric ester zinc, zinc laurate as auxiliary product stripping
Solidification rate and solidification effect in moulding compound process improve modified phenolic molding compound bending modulus, impact strength and drawing
Stretch intensity；
4. filler is modified conch meal, surface and a large amount of micropore of internal formation and micro channel, it is living to remain with conch meal surface
Property hydroxyl, improve dispersion effect of the conch meal in phenolic resin, and improve the binding force of conch meal and phenolic resin, enhancing
Conch meal is to the reinforcing effect of modified phenolic molding compound, and reduces modified phenolic molding compound density；
5. pigment be titanate ester crosslinking agent after inorganic powder pigment, compared with organic coupling agent be organo silane coupling agent when, change
Plastics bending modulus, the impact strength of property phenolic resin are improved；
6. a kind of preparation method of the modified phenolic molding compound of high bending strength, 2- formoxyl -3,4- dihydropyran elder generation and thermosetting
Property phenolic resin hybrid reaction after, add polyvinyl alcohol reaction, adding demoulding auxiliary agent, filler, pigment is mixed,
It improves 2- formoxyl -3,4- dihydropyran and is incorporated into the probability on the cross-linking system of phenolic resin, improve 2- formoxyl -3,4- bis-
The performance improvement of synergistic effect between hydrogen pyrans and polyvinyl alcohol to modified phenolic molding compound.
Specific embodiment
Embodiment one,
A kind of modified phenolic molding compound of high bending strength, modified phenolic molding compound include the following raw material by mass fraction:
200 parts of thermosetting phenolic resin,
4-6 parts of 2- formoxyl -3,4- dihydropyran,
3-5 parts of polyvinyl alcohol,
0.2-4 parts of demoulding auxiliary agent,
7-12 parts of filler,
2-3.5 parts of pigment,
Wherein thermosetting phenolic resin is the thermosetting phenolic resin of liquid.
Thermosetting phenolic resin can be commercial product or voluntarily prepare, and voluntarily prepare as follows:
Phenol and the addition reactor of basic catalyst (NaOH or KOH) in mass ratio 1: 0.05, then phenol in molar ratio: formaldehyde=
To be added formaldehyde, reacted at 1: 1.5, and reaction temperature is 95-110 DEG C, reaction time 1h, is then depressurized and is sloughed after first normal pressure
Moisture and unreacted raw material, obtain the thermosetting phenolic resin of liquid.
2- formoxyl -3,4- dihydropyran is Jin Jinle (Hunan) Chemical Co., Ltd. commercial product.
Polyvinyl alcohol molecule amount is 18000-20000, is existing commercial product.
Demoulding auxiliary agent is one of zinc citrate, cocounut oil alcohol sulfuric ester zinc, zinc laurate, zinc citrate, lauric alcohol sulphur
Acid esters zinc, zinc laurate are commercial product.
Filler is modified modification conch meal.By the aqueous solution soaking conch meal of 14wt% containing NaOH and urea 8wt%,
And be cooled to -14 or less and freeze 10min, melt in heating, after multigelation 3-4, washing drains to obtain.And obtained modification
Conch meal is sieved, and 2 ± 0.1 μm of partial size of powder is obtained.
Pigment is Anthraquinones organic pigment or organic coupling agent treated inorganic powder pigment, and organic coupling agent is metatitanic acid
Esters crosslinking agent is herein three iso stearate isopropyl titanates, is commercial product.Anthraquinones organic pigment is Germany Lang Shengmagao
Arrange the Blue RR of this production.Inorganic powder pigment is that commercial product is carbon black, is commercial product.
A kind of preparation method of the modified phenolic molding compound of above-mentioned high bending strength is as follows:
S1: mass fraction weighs 200 parts of thermosetting phenolic resin of liquid, 4-6 parts of 2- formoxyl -3,4- dihydropyran, poly- second
3-5 parts of enol, 0.2-4 parts of demoulding auxiliary agent, 7-12 parts of filler, 2-3.5 parts of pigment, 10 parts of water, 10 parts of ethyl alcohol；
S2: by 4-6 parts of 2- formoxyl -3,4- dihydropyran and 200 parts of addition stirred reactors of thermosetting phenolic resin, then plus
Enter 1-2 sodium hydroxide, heating stirring, heating temperature is 95-100 DEG C, mixing time 10-30min, obtains liquid or thick shape
Mixture A；
S3: by 10 parts of 3-5 parts of polyvinyl alcohol, 10 parts of water, ethyl alcohol addition mixture A, continue to keep heating temperature to be 125 DEG C, stir
After mixing 20-30min, moisture and other small molecule by-products are sloughed in vacuum distillation after first normal pressure, obtain gelatinous mixture B；
S4: by 0.2-4 parts of demoulding auxiliary agent, 7-12 parts of filler, 2-3.5 parts of pigment and the resulting mixture B of S3 are mixed, in plastics processing mill
Upper to carry out semi-curing processing, low temperature roller temperature is 70-90 DEG C, and high temperature roller temperature is 140-160 DEG C, roll spacing 1.5-2m, when
Between 2-3min, obtain sheet products, crushing obtains a shape or powder product.
It is modified the preparation of phenolaldehyde moulding compound according to above-mentioned preparation method, obtains embodiment 1A-1F.Described modification
Phenolaldehyde moulding compound is at 170-175 DEG C of temperature parameter, and pressure parameter is the pressure forming machine injection-compression molding of 20Mpa, and corresponding
Die for molding obtains test sample of different shapes.
The design parameter of embodiment 1A-1F is as follows.
To the progress of the resulting sample of embodiment one, test result is as follows.
Comparative example one,
A kind of modified phenolic molding compound of high bending strength, based on the basis of embodiment 1B, difference place is 2- formoxyl-
3,4- dihydropyran dosages are 0.
Comparative example two,
A kind of modified phenolic molding compound of high bending strength, based on the basis of embodiment 1B, difference place is with commercially available
3,4- dihydro -2H- pyrans substitute 2- formoxyl -3,4- dihydropyran, and dosage is identical.
Comparative example three,
A kind of modified phenolic molding compound of high bending strength, based on the basis of embodiment 1B, difference place is with commercially available
Cyclohexene substitutes 2- formoxyl -3,4- dihydropyran, and dosage is identical.
Comparative example four,
A kind of modified phenolic molding compound of high bending strength, based on the basis of embodiment 1B, difference place is polyvinyl alcohol
Dosage is 0.
Comparative example five,
A kind of modified phenolic molding compound of high bending strength, based on the basis of embodiment 1B, difference place is that polyethylene replaces
For polyvinyl alcohol, dosage is identical.
Comparative example six,
A kind of modified phenolic molding compound of high bending strength, based on the basis of embodiment 1B, difference place is polyvinyl alcohol
Dosage and 2- formoxyl -3,4- dihydropyran dosage are 0.
To comparative example one to the resulting sample of comparative example five progress, test result is as follows.
Comparative example one, comparative example one are to comparative example five it is found that hydroxyl and 2- formoxyl -3,4- bis- on polyvinyl alcohol
The epoxy bond adjacent with carbon-carbon double bond on hydrogen pyrans so that polyvinyl alcohol and 2- formoxyl -3,4- dihydropyran pass through it is intermolecular
It interacts and combines, generate synergistic effect, reinforce the internal bond strength of phenolaldehyde moulding compound；Final resulting modified phenolic molding
For expecting more existing unmodified and big brittleness phenolaldehyde moulding compound, mechanical property is improved, tensile strength, bending strength and punching
Hit intensity is improved, and while reducing modified phenolic molding compound brittleness, obtains the raising on rigidity and toughness properties.
Embodiment two,
A kind of modified phenolic molding compound of high bending strength, based on the basis of embodiment 1B, difference place is demoulding auxiliary agent
For one of commercially available stearic acid, calcium stearate, zinc stearate, magnesium stearate, demolding aids mass fraction is 0.2-0.4
Part.
| Embodiment 2A | Embodiment 2B | Embodiment 2C | Embodiment 2D | |
| Demoulding auxiliary agent | Stearic acid | Calcium stearate | Zinc stearate | Magnesium stearate |
To the progress of the resulting sample of embodiment two, test result is as follows.
| Examination criteria | Embodiment 2A | Embodiment 2B | Embodiment 2C | Embodiment 2D | |
| Specific gravity/gcm-3 | - | 1.79 | 1.79 | 1.79 | 1.79 |
| Tensile strength/MPa | TS-INT-002 | 122 | 124 | 130 | 125 |
| Bending strength/MPa | GB T 9341-2008 | 192 | 197 | 198 | 196 |
| Bending modulus/GPa | GB T 9341-2008 | 16.53 | 16.61 | 16.65 | 16.63 |
| Impact strength/KJm-2 | ASTM D256-2010E1 | 16.6 | 16.8 | 17 | 16.9 |
| TVOC/μg·g-1 | TS-INT-002 | 43 | 42 | 43 | 46 |
Comparative example one and embodiment two are it is found that hydroxyalkyl reaction forming phenol in hydroxyl and phenolic resin on polyalkenylalcohols
When urea formaldehyde cross-linking system, the processing performance of phenolic resin is improved, mobility when phenolic resin melting is improved, reduces
The adhesive of product after cooling reduces to the single release agent dosage for promoting modified phenolic molding compound, reduces auxiliary dosage, reduces
The internal remaining possibility of small molecule after modified phenolic molding compound use, for being applicable in the engineering plastics required to VOC.
Zinc citrate, cocounut oil alcohol sulfuric ester zinc, zinc laurate are convenient for product stripping in the processing performance for improving phenolic resin
While, it more can adequately be mixed with liquid or thick thermosetting phenolic resin, so that zinc citrate, lauric alcohol sulphur
Divalent zinc in acid esters zinc, zinc laurate can play the role of curing accelerator, promote in modified phenolic molding compound process
Solidification rate and solidification effect, improve modified phenolic molding compound bending modulus, impact strength and tensile strength.
Embodiment three,
A kind of modified phenolic molding compound of high bending strength, based on the basis of embodiment 1B, difference place is that filler is city
The non-high-temperature calcination sold or the conch meal being heated at high temperature.
Example IV,
A kind of modified phenolic molding compound of high bending strength, based on the basis of embodiment 1B, difference place is that filler is city
The high-temperature calcination sold or the conch meal being heated at high temperature.
Embodiment five,
A kind of modified phenolic molding compound of high bending strength, based on the basis of embodiment 1B, difference place is modified shell
Powder diameter is 1.0-2.5 μm.
| Embodiment 5A | Embodiment 5B | Embodiment 5C | |
| Modified conch meal partial size/μm | 1.0 | 1.5 | 2.5 |
To embodiment three to the resulting sample of embodiment five progress, test result is as follows.
| Examination criteria | Embodiment three | Example IV | Embodiment 5A | Embodiment 5B | Embodiment 5C | |
| Specific gravity/gcm-3 | - | 1.81 | 1.79 | 1.78 | 1.78 | 1.78 |
| Tensile strength/MPa | TS-INT-002 | 125 | 126 | 130 | 132 | 136 |
| Bending strength/MPa | GB T 9341-2008 | 205 | 208 | 212 | 210 | 206 |
| Bending modulus/GPa | GB T 9341-2008 | 17 | 17 | 16.5 | 16.8 | 17 |
| Impact strength/KJm-2 | ASTM D256-2010E1 | 16.3 | 16.5 | 17.3 | 17.35 | 17.35 |
| TVOC/μg·g-1 | TS-INT-002 | 74 | 75 | 75 | 75 | 75 |
Modified conch meal is handled by the aqueous solution soaking conch meal and multigelation of NaOH 14wt% and urea 8wt%,
The chitin in conch meal is removed, on conch meal surface and a large amount of micropore of internal formation and micro channel, while avoiding high temperature
The removal to conch meal surface-active hydroxyl is handled, improves dispersion effect of the conch meal in phenolic resin, and improve shell
The binding force of powder and phenolic resin enhances conch meal to the reinforcing effect of modified phenolic molding compound, and reduces modified phenolic mould
Plastic density.
Embodiment six,
A kind of modified phenolic molding compound of high bending strength, based on the basis of embodiment 1B, difference place is that carbon black uses
Organo silane coupling agent processing, organo silane coupling agent are silane coupling agent KH-560.
To the progress of the resulting sample of embodiment six, test result is as follows.
It is found that pigment selects inorganic powder pigment, organic coupling agent is titanate ester for comparative example one and embodiment six
When crosslinking agent, phenol-formaldehyde resin modified compared with organic coupling agent be organo silane coupling agent when, the plastics bending die of phenol-formaldehyde resin modified
Amount, impact strength are improved.
Embodiment seven,
A kind of preparation method of the modified phenolic molding compound of high bending strength is as follows:
S1: mass fraction weighs the thermosetting phenolic resin of liquid, 2- formoxyl -3,4- dihydropyran, polyvinyl alcohol, demoulding and helps
Agent, filler, pigment, 10 parts of water and 10 parts of ethyl alcohol；
S2: stirring is added instead in 4-6 parts of 2- formoxyl -3,4- dihydropyran, polyvinyl alcohol, water, ethyl alcohol, thermosetting phenolic resin
It answers in device, adds 1-2 sodium hydroxide, heating stirring, heating temperature is 95-100 DEG C, and mixing time 30-60min is obtained
The mixture C of liquid or thick shape；
S4: demoulding auxiliary agent, filler, pigment and the resulting mixture C of S3 being mixed, semi-curing processing is carried out on plastics processing mill, low
Warm roller temperature is 70-90 DEG C, and high temperature roller temperature is 140-160 DEG C, roll spacing 1.5-2m, time 2-3min, obtains sheet production
Product, crushing obtain a shape or powder product.
To the progress of seven gained sample of embodiment, test result is as follows.
Comparative example one and embodiment seven are it is found that 2- formoxyl -3,4- dihydropyran is first mixed with thermosetting phenolic resin
After closing reaction, polyvinyl alcohol reaction is added, demoulding auxiliary agent, filler, pigment is added and is mixed, guarantees 2- formyl
The aldehyde radical of base -3,4- dihydropyran is first reacted with the phenolic hydroxyl group of phenolic resin, avoids hydroxyl and 2- formoxyl-on polyvinyl alcohol
The aldehyde radical of 3,4- dihydropyran reacts and 2- formoxyl -3,4- dihydropyran is hindered to be incorporated on the cross-linking system of phenolic resin,
It improves 2- formoxyl -3,4- dihydropyran and is incorporated into the probability on the cross-linking system of phenolic resin, improve 2- formoxyl -3,4- bis-
The performance improvement of synergistic effect between hydrogen pyrans and polyvinyl alcohol to modified phenolic molding compound.
Above-mentioned specific embodiment is only explanation of the invention, is not limitation of the present invention, art technology
Personnel can according to need the modification that not creative contribution is made to the present embodiment after reading this specification, but as long as
All by the protection of Patent Law in scope of the presently claimed invention.
Claims (9)
1. a kind of modified phenolic molding compound of high bending strength, which is characterized in that the modified phenolic molding compound includes pressing quality
The following raw material of number:
200 parts of thermosetting phenolic resin,
4-6 parts of 2- formoxyl -3,4- dihydropyran,
3-5 parts of polyvinyl alcohol,
0.2-4 parts of demoulding auxiliary agent,
7-12 parts of filler,
2-3.5 parts of pigment,
Wherein thermosetting phenolic resin is the thermosetting phenolic resin of liquid.
2. a kind of modified phenolic molding compound of high bending strength according to claim 1, which is characterized in that the polyethylene
Alcohol is POLYPROPYLENE GLYCOL.
3. a kind of modified phenolic molding compound of high bending strength according to claim 1, which is characterized in that the demoulding helps
Agent is one of stearic acid, calcium stearate, zinc stearate, magnesium stearate or a variety of, and the demolding aids mass fraction is
0.2-0.4 parts.
4. a kind of modified phenolic molding compound of high bending strength according to claim 1, which is characterized in that the demoulding helps
Agent is one of zinc citrate, cocounut oil alcohol sulfuric ester zinc, zinc laurate or a variety of, and the demolding aids mass fraction is 2-4
Part.
5. a kind of modified phenolic molding compound of high bending strength according to claim 1, which is characterized in that the filler is
Modified conch meal, the modified conch meal by 14wt% containing NaOH and urea 8wt% aqueous solution soaking conch meal and freeze repeatedly
After melting processing, washing drains to obtain.
6. a kind of modified phenolic molding compound of high bending strength according to claim 1, which is characterized in that the modified shellfish
Shell powder diameter is 1.0-2.5 μm.
7. a kind of modified phenolic molding compound of high bending strength according to claim 1, which is characterized in that the pigment is
Anthraquinones organic pigment or organic coupling agent treated inorganic powder pigment.
8. a kind of modified phenolic molding compound of high bending strength according to claim 7, which is characterized in that the pigment is
Organic coupling agent treated inorganic powder pigment, the organic coupling agent are titanate ester crosslinking agent.
9. a kind of preparation method of the modified phenolic molding compound of high bending strength, which comprises the following steps:
S1: weighing 200 parts of thermosetting phenolic resin, 4-6 parts of 2- formoxyl -3,4- dihydropyran, and 3-5 parts of polyvinyl alcohol, demoulding
0.2-4 parts of auxiliary agent, 7-12 parts of filler, 2-3.5 parts of pigment, wherein thermosetting phenolic resin is the thermosetting phenolic resin of liquid；
S2: by 4-6 parts of 2- formoxyl -3,4- dihydropyran and 200 parts of addition stirred reactors of thermosetting phenolic resin, then plus
Enter 1-2 sodium hydroxide, heating stirring, heating temperature is 95-100 DEG C, mixing time 10-30min, obtains liquid or thick shape
Mixture A；
S3: 3-5 parts of addition mixture A of polyvinyl alcohol continue to keep heating temperature to be 95 DEG C, after stirring 40-60min, often first
Moisture and other small molecule by-products are sloughed in vacuum distillation after pressure, obtain gelatinous mixture B；
S4: by 0.2-4 parts of demoulding auxiliary agent, 7-12 parts of filler, 2-3.5 parts of pigment and the resulting mixture B of S3 are mixed, in plastics processing mill
Upper to carry out semi-curing processing, low temperature roller temperature is 70-90 DEG C, and high temperature roller temperature is 140-160 DEG C, roll spacing 1.5-2m, when
Between 2-3min, obtain sheet products, crushing obtains a shape or powder product.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113321897A (en) * | 2021-06-18 | 2021-08-31 | 上海欧亚合成材料股份有限公司 | Phenolic molding plastic with high bending strength and preparation method thereof |
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| CN101781441A (en) * | 2009-01-21 | 2010-07-21 | 上海欧亚合成材料有限公司 | Phenolic moulding plastics for commutator |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113321897A (en) * | 2021-06-18 | 2021-08-31 | 上海欧亚合成材料股份有限公司 | Phenolic molding plastic with high bending strength and preparation method thereof |
| CN113321897B (en) * | 2021-06-18 | 2022-07-12 | 上海欧亚合成材料股份有限公司 | Phenolic molding plastic with high bending strength and preparation method thereof |
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