CN1131136C - Mfg. method of phenolic resin shaping material containing little or no free ammonia - Google Patents
Mfg. method of phenolic resin shaping material containing little or no free ammonia Download PDFInfo
- Publication number
- CN1131136C CN1131136C CN99100034A CN99100034A CN1131136C CN 1131136 C CN1131136 C CN 1131136C CN 99100034 A CN99100034 A CN 99100034A CN 99100034 A CN99100034 A CN 99100034A CN 1131136 C CN1131136 C CN 1131136C
- Authority
- CN
- China
- Prior art keywords
- self
- resin
- hardening property
- free ammonia
- resol
- 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.)
- Expired - Lifetime
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention provides a method for preparing the molding materials of phenolic resin, and the molding materials do not contain free ammonia or contain low content of free ammonia. In the method, liquid or solid self-hardening phenolic resin (commonly called resol) with a molecular structure containing more than one hydroxymethyl functional group, modified resin of the liquid or solid self-hardening phenolic resin, or liquid or solid amine resin with a molecular structure containing more than one hydroxymethyl functional group or modified resin of the liquid or solid amine resin is used for cooperating with non self-hardening phenolic resin (commonly called novolac resin) for carrying out crosslinking reaction. In the method for preparing the molding materials of phenolic resin of the present invention, even if liquid resin is used as raw materials, the materials of a formula can be directly mixing at a semidried pudgy state after blending in a common blender, and a drying process in a conventional technology can be omitted.
Description
Technical field
The present invention relates to a kind of manufacture method of resol formed material.
Background technology
The manufacturing of past resol formed material, cooperate with vulkacit H with the non-self-hardening property resol of solid mostly, as fibrous materials such as wood powder and inorganic filler such as talcum powder, lime carbonate, glass fibre, mica powder etc., and add after parting agent, flame retardant and the colorant etc., through raw material pulverizing, mix, mix, operation manufacturing such as cooling, granulation and getting.Because this kind method must use vulkacit H as stiffening agent in operation, and this stiffening agent can disengage a large amount of ammonia gas after thermal degradation, therefore can cause heavy corrosion to the lead on the electric parts.In recent years, the resol formed material is applied in the moulding of electric parts, and usage quantity continue to rise, and quality requirements also constantly promotes, therefore, and low ammonia emission or even not have the first-class resol formed material that ammonia disengages be the ardent hope of institute of moulding manufacturer.
At present, existing on the market no free ammonia or contain the resol formed material of low amount free ammonia (free ammonia content is called in the resol formed material finished product contain the low free ammonia of measuring) below 100ppm, its manufacture method all use haply can be divided on self-hardening property resin and the technology following several.One directly cooperates fibrous material such as wood powder and mineral filler, parting agent, flame retardant, colorant etc. for using solid self-hardening property resin, similar to the manufacture method of traditional resol formed material, be referred to as drying process, each composition raw material all is under the solid dry type state directly pulverize, mixes, mixes, cooling, granulation mode and make, open flat 6-322238 and the disclosed technology of 7-118501 as the patent documentation spy.The shortcoming of this kind technology is for using solid self-hardening property resin, it is produced difficult and costs an arm and a leg, this resin easily sclerosis in process of production again, its softening temperature can't be increased to the softening temperature as non-self-hardening property resol, so resin stores and use in easy caking and not easy to operate.Another kind of production technique then is to utilize solvent type liquid self-hardening property resin, in this method, because of resin is a liquid, therefore this resin general earlier with prescription in cellulose raw material through impregnation, drying after, again with solid material such as inorganic filler, parting agent, flame retardant, colorant etc. according to above-mentioned drying process mix, mix, modes such as cooling, granulation make; Or liquid resin raw material and raw materials such as other solid filling materials, additive in the above-mentioned prescription are added in the lump mix simultaneously, mix in the Special Mixed machine of similar positive mixer class and operation such as drying after, again through cooling, granulation stage and make finished product, the i.e. damp process that is referred to as.This utilizes the technology of liquid self-hardening property resin such as the patent documentation spy opens clear 64-1714 and the spy opens the disclosed technology of flat 4-318053.This utilizes the technology of liquid self-hardening property resin can overcome the puzzlement of aforementioned solid self-hardening property production of resins difficulty, but need have more the step that makes solvent seasoning together, and the technology cost is increased.Moreover this technology if employed liquid self-hardening property resin reaction molecular weight is too little, between its dry epoch, causes foul smell and toxicity because of residual a large amount of free phenols in the resin reach free formalin easily; If liquid self-hardening property molecular resin is aggregated to a certain degree, can produce the albefaction layering, must be by after organic solvent diluting, the dissolving, just can carry out impregnation mixes, and these organic solvents during drying can be discharged a large amount of volatile organic matters (volatile organic compouad, VOC) and contaminate environment and human body worked the mischief is also undesirable in the production.
Summary of the invention
The objective of the invention is to overcome the shortcoming in the aforesaid method, a kind of manufacture method that does not contain free ammonia or contain the resol formed material of low amount free ammonia is provided.
Another purpose of the present invention is to provide a kind of not containing free ammonia or containing the low manufacture method of measuring the resol formed material of free ammonia of drying step of with an organic solvent and not need not utilizing.
The invention provides a kind of manufacture method that does not contain free ammonia or contain the resol formed material of low amount free ammonia, this method comprises utilizes liquid or liquid and solid phenolic aldehyde self-hardening property resin [being commonly called as solvable phenolic aldehyde (resol) resin] or its denatured resin that contains an above methylol functional group in the molecular structure, or utilize liquid or liquid and solid amine resin or its denatured resin that contains an above methylol functional group in the molecular structure, cooperate and carry out crosslinking reaction with non-self-hardening property resol [being commonly called as phenolic varnish (novolac) resin].
In the manufacture method of the present invention, use the liquid self-hardening property resin of non-organic solvent type to use separately or with other solid self-hardening property resin combination, heat with non-self-hardening property resol and to mix and polymerization, rely on the non-self-hardening property resol self-hardening property resin direct and of larger molecular weight to react to each other, and make molecular weight obtain rapidly to grow up than small molecular weight.
There is no particular restriction for the non-self-hardening property resol that uses among the present invention, as long as record softening temperature more than 75 ℃ with JIS K 7234 described ring and ball methods.Can use general commercially available non-self-hardening property resol or phenol denatured resin.
The self-hardening property resol that contains an above methylol functional group that uses among the present invention is to be reacted in the presence of catalyzer and got by phenolic compound, urea or trimeric cyanamide or similar derivative thing and formaldehyde or formaldehyde derivatives.Formaldehyde or formaldehyde derivatives (following table is shown F) are required to be more than 0.8 to phenolic compound (following table is shown P) or to the mol ratio F/P or the F/M of amido material (following table is shown M) during reaction, are preferably 0.8 to 6.0, and more preferably 1.0～3.0.
Catalyst system therefor is the oxide compound or the oxyhydroxide of periodic table of elements I, II family basic metal, alkaline-earth metal for example, or ammonia soln or amine compound or ammonium salt etc.This catalyzer can use or merge two or more uses separately.And catalyst levels is below 3% to the weight ratio of phenolic compound.
Range of reaction temperature can be between 40 ℃ to 100 ℃, and reaction process has water-soluble based on the control resin; Reaction raw materials is reacted after reach required gel time (gel time) in stirring under this temperature of reaction, is reaction end, and can removing partly down in decompression this moment, moisture promptly gets liquid self-hardening property resin to required solid shape branch (being preferably more than 40 nitriles).So-called gel time that is according to JIS K6909 method, on hot plate to not producing the stringy time.
Above-mentioned self-hardening property resin is if continue to react to tool specified molecular weight (generally tie up to 50-200 ℃ thermotonus about 0.5 to 5 hour) in step of reaction, cooperate decompression dehydration again, in below 100 ℃, release quick cooling after being evacuated to specific softening temperature of tool or gel time, be solid self-hardening property resin.
The main characteristic of the manufacture method of resol formed material of the present invention mixes in the partial desiccation mode for being used above-mentioned self-hardening property resol and non-self-hardening property resol.
In the inventive method, used self-hardening property resol there is no particular restriction to the ratio of non-self-hardening property resin, but generally be controlled in the scope of (F/P or F/M mol ratio during the hard resin reaction of the shared full resin ratio of hard resin of F/P mol ratio during the ratio of the shared full resin of non-self-hardening property resol * non-self-hardening property reactive modified phenolic resin+separately * separately) 〉=1.0, and all raw materials still are in the half dry type state in can keeping filling a prescription in mixing engineering, and can not cause caking or influence operability is principle.The reaction mole fraction summation of used resin needs more than 1.0, its objective is the formaldehyde (F) of serving as the bridge formation role in the resin is needed more than phenolic compound (P) or trimeric cyanamide or urea (M), just can produce crosslinked (crosslinking) sclerosis.Wherein, described phenolic compound is preferably phenol, C
1-4Monoalkyl phenol or C
1-4Dialkyl phenol or its mixture.
In the inventive method, make above-mentioned non-self-hardening property resol and self-hardening property resin and lignocellulosic material, inorganic additives, parting agent, flame retardant, colorant etc. directly in general mixing machine, the state of still unlikely generation caking mixes with partial desiccation; Directly mix subsequently, cooling and granulation stage, and make the resol formed material.
Employed liquid resin is preferably water-soluble non-organic solvent type in the inventive method, and contained humidity volatilization naturally under heated condition in the operation of mixing in it, and reach the trimmed size requirement.
Specifically, in the inventive method, make above-mentioned resin cooperate fibrous material and mineral filler such as lime carbonate, talcum powder, mica, Calucium Silicate powder or glass fibre and so on such as wood powder, paper powder, and colorant, parting agent, flame retardant, promotor etc., after evenly mixing in mixing whipping device such as ball mill, positive mixer or the similar devices, to mix test portion and leak in cylinder machine or the extruder and mix, the test portion after mixing is broken into the particulate state finished product with pulverizer after the cold wind blast-cold.
The inventive method is in operation if when not using vulkacit H, (promptly is called no free ammonia) through the free ammonia content of the resol moulding product behind the ejection formation below 10ppm; And in operation if when using the vulkacit H of restriction total amount 2% below, (promptly be called to contain to hang down and measure free ammonia) below 100ppm through the free ammonia content of the moulding product behind the ejection formation.
The inventive method can solve solid type self-hardening property production of resins difficulty simultaneously and damp process technology needs drying to cause the puzzlement of deleterious organic gas generation.
Embodiment
Following examples and Production Example are described in more detail the present invention, but not in order to limit the scope of the invention.
The preparation embodiment 1 of self-hardening property resol:
Make phenol 940 grams, 37% formalin, 2000 grams, 50% aqueous sodium hydroxide solution, 5.0 grams place the glass reaction still, through 60～70 ℃ of reacting by heating after 1 hour, decompression dehydration and add acetic acid 1.8 gram neutralizations after can make solid shape and divide 85% and about 2000 grams of liquid self-hardening property resin of gel time 2 minutes 30 seconds (surveying down for 150 ℃).
Embodiment 2:
With the prescription of embodiment 1, after finishing, reaction, can make softening temperature 80 ℃ of (ring and ball method) and about 1700 grams of 60～70 seconds solid self-hardening property resin of gel time at last in 90 ℃ of decompression continuation dehydrations down.
Embodiment 3:
Make phenol 752 grams, meta-cresol (m-Cresol) 216 grams, 37% formalin, 2000 grams, the mixture of calcium oxide 2 grams, reaction process with embodiment 1 reacts, and can make that solid shape divides 85%, about 2000 grams of the liquid self-hardening property resin of gel time 3 minutes (recording under 150 ℃).
Embodiment 4:
Make phenol 940 grams, 37% formalin, 1500 grams, furfural 592 grams, triethyl diamines (Triethylenediamine) 10 grams, with reaction conditions and technological reaction, can make that solid shape divides 85, the liquid self-hardening property resin of gel time 3 minutes 30 seconds (recording under 150 ℃) 2000 grams with embodiment 1.
Embodiment 5:
37% formalin 1000 gram, trimeric cyanamide 750 grams, 28% ammonia soln, 10 grams place the glass reaction still through 100 ℃ of reacting by heating after 2 hours, after the decompression vacuum pumping dehydration, can make softening temperature 90 ℃ of (ring and ball method) and 2 minutes 30 seconds solid self-hardening property resin of gel time, 1150 grams.
Embodiment 6:
Phenol 940 grams, 37% formalin, 648 grams, oxalic acid 9.4 grams place the glass reaction still, heat 100 ℃ of reactions after 3 hours, vacuumize and be warming up to 150 ℃ of blowdowns, can make non-self-hardening property resol (Novlac) 1000 grams of softening temperature 100 ℃ (ring and ball methods).
The preparation of resol formed material
Embodiment 7:
Non-self-hardening property resol 150 weight parts of embodiment 6
Liquid self-hardening property resin 100 weight parts of embodiment 1
Wood powder 160 weight parts
Calcium hydroxide 25 weight parts
Talcum powder 110 weight parts
Magnesium Stearate 15 weight parts
Black material 10 weight parts
Above-mentioned raw materials normal temperature in positive mixer mixes fast and leaks in the cylinder machine heating after 20 minutes and mix, and the good test piece of mixing is smashed with quick pulverizer (Speed Mill) after the cold wind blast-cold and made the particulate state finished product.
Embodiment 8:
Non-self-hardening property resol 150 weight parts of embodiment 6
Liquid self-hardening property resin 50 weight parts of embodiment 3
Solid self-hardening property resin 50 weight parts of embodiment 2
Wood powder 160 weight parts
Calcium hydroxide 25 weight parts
Talcum powder 110 weight parts
Magnesium Stearate 15 weight parts
Black material (SB) 10 weight parts
Above raw material is made the particulate state finished product as embodiment 7 methods.
Embodiment 9:
Non-self-hardening property resol 150 weight parts of embodiment 6
Liquid self-hardening property resin 50 weight parts of embodiment 4
Solid self-hardening property resin 50 weight parts of embodiment 5
Wood powder 160 weight parts
Calcium hydroxide 25 weight parts
Talcum powder 110 weight parts
Magnesium Stearate 15 weight parts
Black material (SB) 10 weight parts
Above raw material is made the particulate state finished product as embodiment 7 methods.
Embodiment 10:
Non-self-hardening property resol 175 weight parts of embodiment 6
Liquid self-hardening property resin 75 weight parts of embodiment 1
Vulkacit H 10 weight parts
Wood powder 160 weight parts
Calcium hydroxide 25 weight parts
Talcum powder 110 weight parts
Magnesium Stearate 15 weight parts
Black material (SB) 10 weight parts
Above raw material is made the particulate state finished product as embodiment 7 methods.
Comparative example 1:
Non-self-hardening property resol 230 weight parts
Vulkacit H 45 weight parts
Wood powder 160 weight parts
Calcium hydroxide 25 weight parts
Talcum powder 110 weight parts
Magnesium Stearate 15 weight parts
Black material (SB) 10 weight parts
Above raw material leaks into after ball mill mixes 1 hour and mixes in the cylinder machine and make the particulate state finished product according to embodiment 6.
Comparative example 2:
Make solid shape with the reactive mode of embodiment 1 and divide 50% liquid self-hardening property resin 100 weight parts, add paper pulp 25 weight parts after, in 80 ℃ of oven dry 3 hours, can make dry thing A after kneader is mediated 30 minutes and through baking oven.
Dry thing A 345 weight parts
Talcum powder 110 weight parts
Calcium hydroxide 25 weight parts
Magnesium Stearate 15 weight parts
Black material (SB) 10 weight parts
Above resol formula material after pulverizing mixing in the ball mill, is made particulate state phenolic resin material finished product according to aforementioned manner according to comparative example 1 mode.
Test case
The property detection of the phenolic resin material that the inventive method makes records according to following method
1. mobile: as under may command fixed temperature (170 ℃), to pour quantitative test portion (40g) into and in the spirrillum mould of mosquito-repellent incense shape, impose certain pressure (gauge pressure 100kg/cm
2), behind hardened material, read the mobile length of mosquito-repellent incense shape test portion hardening thing.
2. shock strength: utilizing Jet forming machine moulding specification is 90 * 15 * 15m/m test piece, calculates shock strength according to JIS K7111 test mode and computing method again.
3. folding strength: utilize Jet forming machine to manufacture more than the long 80m/m according to JIS K7203, thick (height) 4 ± 0.2m/m, the standard test piece of wide 10 ± 0.5m/m with trier and according to its formula of being devised a stratagem, calculate folding strength more than 5 again.
4. anti-electric arc: according to JIS K6911 mode moulding φ 100m/m, thick 3.0 ± 0.25m/m test piece, anti-electric arc number second is measured in test piece and after C-91 ± 3h/20 ± 2 ℃/65 ± 5%RH condition pre-treatment in trier.
5. dielectric strength: test piece specification 100m/mID, the thick test piece of 2 ± 0.3m/m with C-91 ± 3h/20 ± 2 ℃/65 ± 5%RH pre-treatment after, record dielectric strength according to JIS K6915 method.
6. insulation strength: according to JIS K691547 content manufacture size 20m/m * 40m/m * 10m/m thick * hole φ 5m/m, pitch-row 15m/m test piece detects insulation opposing value.
7. heat resisting temperature: manufacture ID50 ± 1m/m according to JIS K6911, thick 3 ± 0.2m/m test piece in baking oven 2 hours, test the upper limit temperature of heat tolerance.
8. thermal change type: manufacture wide 6.4 ± 0.2m/m according to JIS K7207, high 12.7 ± 0.2m/m, the above test piece of long 110m/m heats up in oil groove and after adding continuous load, records test piece temperature when reaching certain modification amount.
9. free ammonia
9.1 use reagent:
9.1.1Nesseler reagent:
Get the 50g potassiumiodide and make it dissolving with minimum water (not containing free ammonia), the saturated solution that adds mercury chloride adds the mixing of 50% potassium hydroxide solution again and pours above-mentioned solution into 1 liter flask up to there being undissolved precipitation to take place, and is diluted with water to 1 liter and ends, leave standstill and make precipitation, get upper strata liquid and use.
9.1.2 ammonia standardized solution:
Get ammonia chloride in 100 ℃ of baking ovens dry one hour, smartly claim 3.14 liters and be dissolved in 1 liter of ultrapure water, get above-mentioned solution 10ml again and be diluted to 1 liter (NH3=0.01mg/ml).
9.1.3 inspection amount line is made:
Get 49,48,47,46 respectively, 45ml ultrapure water and above-mentioned ammonia reference liquid 1,2,3,4,5ml adds 2mlNesseler reagent simultaneously in Erlenmeyer flask, make inspection amount line with wavelength 425nm.
9.2 determination step:
9.2.1 weigh after leaving standstill more than 16 hours in the air-conditioning room after the about 8-10g moulding of test portion, test piece is (50 ± 1) mm φ * (3 ± 1) mm.
9.2.2 adjust 50 ± 2 ℃ in baking oven.
9.2.3 add 250ml distilled water in 1 liter of container and put into test piece warm 2 hours ± 5 minutes at baking oven.
Get extraction liquid 10ml 9.2.4 be cooled to room temperature, add 2%NaOH 10ml and 0.02gKMnO
4(potassium permanganate) with till being purple, and insert 2～3 heulandites.
9.2.5, get initial distillate 10ml and be diluted to 50ml and add 2mlNesseler reagent simultaneously, with wavelength 425nm colorimetric with the distillation of above-mentioned solution.
9.3 calculate:
AS: the free ammonia to breaking forth on the inspection amount line, mg (10
-3G)
D: dilutionization coefficient (is 25 at this) before the sample liquid distillation
S: sample is heavy, g
10. gel time: record according to JIS K6909 method.
11. softening Lu's (ring and ball method): record according to JIS K7234 method.
Each property detection of finished product of the present invention and comparative example finished product the results are shown in table 1.
Table 1
| Characteristic | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Comparative example 1 | Comparative example 2 |
| Mobile (cm) | 60 | 55 | 65 | 55 | 65 | 66 |
| Shock strength (Chappy lmpact) (kg f * cm/cm * cm) | 4.0 | 4.0 | 4.0 | 3.8 | 4.0 | 3.5 |
| Folding strength (Flexural Strength) (kg f/mm * mm) | 9.5 | 9.5 | 9.5 | 9.5 | 9.0 | 7.5 |
| Anti-electric arc (Arc Resistance) (second) | 120 | 120 | 180 | 120 | 70 | 120 |
| Dielectric strength (Dielectric Strength) (Kv/mm) | 12 | 12 | 12 | 12 | 13 | 10 |
| Insulation opposing (Insulation esistance) is E10 * Ω (N) | 6.0 | 6.0 | 6.0 | 5.0 | 3.6 | 4.0 |
| Thermotolerance (Heat Resistance) (℃) | 200 | 200 | 190 | 190 | 180 | 190 |
| Thermal change type temperature (Deflectioh Temp) (℃) | 200 | 200 | 190 | 19 | 170 | 190 |
| Free ammonia (%) | 0.001＜ | 0.001＜ | 0.001＜ | 0.009 | 0.050 | 0.001＜ |
Comparative example 1 is to use vulkacit H as stiffening agent, and is not used self-hardening property resol, so the free ammonia of moulding product is far above other moulding product.Though and each character of moulding product of comparative example 2 is also excellent, therefore because of comparative example 2 is only used liquid self-hardening property resol, need utilize the technology of damp process, need utilize the exsiccant step again therebetween, therefore more uneconomical and bother consuming time.Though and embodiment 10 uses the vulkacit H that accounts for total amount about 2%, because of it uses non-self-hardening property resin and self-hardening property resin with half dry type technology of the present invention manufacturing simultaneously, its moulding product free ammonia is reduced to 90ppm.And each character of moulding product of other embodiment of the present invention all is better than comparative example 1, and free ammonia content is all below 10ppm.
According to method of the present invention, solved simultaneously and only utilized the shortcoming of producing difficult and expensive solid self-hardening property resin in the drying process technology, and must the drying step in the damp process technology and produce the problem of poisonous organic gas, and also has excellent character according to the phenolic resin material that the inventive method makes.
Claims (6)
1. a manufacturing does not contain free ammonia or contains the low method of measuring the resol formed material of free ammonia, it is characterized by and be used liquid or liquid-solid body blended phenolic aldehyde and/or amido self-hardening property resin and the non-self-hardening property resol that contains 1 above methylol functional group in the molecular structure, behind the direct uniform mixing of other additives, directly carry out mixing, cooling and granulation without drying step, and make the resol formed material that does not contain free ammonia or contain low amount free ammonia; Describedly contain low amount free ammonia and be meant that the content of free ammonia is less than 100ppm;
The usage ratio of wherein non-self-hardening property resol and phenolic aldehyde and/or amido self-hardening property resin, for making [formaldehyde/phenolic compound (F/P) when mol ratio+each phenolic aldehyde of the formaldehyde/phenolic compound (F/P) during the shared % of non-self-hardening property resol * non-self-hardening property reactive modified phenolic resin and/or the shared % of amido self-hardening property resin * each phenolic aldehyde and/or amido self-hardening property resin reaction or the mol ratio of formaldehyde/urea or trimeric cyanamide (F/M)] 〉=1.0, and this phenolic aldehyde and/or amido self-hardening property resin are with phenolic compound, urea or trimeric cyanamide and formaldehyde or derivatives thereof are being selected from basic metal, the oxide compound of alkaline-earth metal or oxyhydroxide, and there is reaction down in the catalyzer of ammoniacal liquor or amine compound or ammonium salt and gets.
2. method according to claim 1 is characterized in that wherein this additive is filamentary material, inorganic additives, parting agent, flame retardant and colorant.
3. method according to claim 1 is characterized in that formaldehyde or derivatives thereof (F) wherein is more than 0.8 to phenolic compound (P) or to the mol ratio (F/P or F/M) of trimeric cyanamide or urea (M).
4. method according to claim 3 is characterized in that wherein F/P or F/M ratio are 0.8 to 6.0.
5. according to the method for claim 4, wherein F/P or F/M ratio are 1.0 to 3.0.
6. according to the process of claim 1 wherein that phenolic compound is a phenol, C
1-4Monoalkyl phenol or C
1-4Dialkyl phenol or its mixture.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99100034A CN1131136C (en) | 1999-01-07 | 1999-01-07 | Mfg. method of phenolic resin shaping material containing little or no free ammonia |
| HK00105895A HK1026666A1 (en) | 1999-01-07 | 2000-09-19 | A process for preparing a phenolic resin molding material containing none or a small amount of free ammonia |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99100034A CN1131136C (en) | 1999-01-07 | 1999-01-07 | Mfg. method of phenolic resin shaping material containing little or no free ammonia |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1259424A CN1259424A (en) | 2000-07-12 |
| CN1131136C true CN1131136C (en) | 2003-12-17 |
Family
ID=5269743
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99100034A Expired - Lifetime CN1131136C (en) | 1999-01-07 | 1999-01-07 | Mfg. method of phenolic resin shaping material containing little or no free ammonia |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN1131136C (en) |
| HK (1) | HK1026666A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100443532C (en) * | 2004-12-18 | 2008-12-17 | 陈天云 | Environment-friendly type plastic and production method thereof |
| CN100457822C (en) * | 2006-10-30 | 2009-02-04 | 林良菽 | Plastic of phenolic aldehyde mould in no ammonia type, and manufacturing method |
| CN101210063B (en) * | 2006-12-30 | 2010-05-19 | 王洁凡 | Granulation formation method in phenol formaldehyde resin production process |
| CN103183904A (en) * | 2011-12-27 | 2013-07-03 | 常熟市亚美模特儿衣架有限公司 | Flame-retardant phenolic resin forming material without ammonia release |
| CN103183915A (en) * | 2011-12-27 | 2013-07-03 | 常熟市亚美模特儿衣架有限公司 | Phenolic composite material filled with metal fibres and without ammonia release |
| US9890130B2 (en) | 2013-02-15 | 2018-02-13 | Empire Technology Development Llc | Phenolic epoxy compounds |
| WO2014200486A1 (en) * | 2013-06-13 | 2014-12-18 | Empire Technology Development Llc | Multi-functional phenolic resins |
| CN105814014B (en) | 2013-12-02 | 2018-06-12 | 英派尔科技开发有限公司 | Novel gemini surfactants and their purposes |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4426484A (en) * | 1980-10-21 | 1984-01-17 | Sumitomo Durez Company, Ltd. | Method for accelerating cure of resole type phenolic resins |
| CN1145927A (en) * | 1995-07-12 | 1997-03-26 | 住友电木株式会社 | Phenolic resin molding material |
-
1999
- 1999-01-07 CN CN99100034A patent/CN1131136C/en not_active Expired - Lifetime
-
2000
- 2000-09-19 HK HK00105895A patent/HK1026666A1/en not_active IP Right Cessation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4426484A (en) * | 1980-10-21 | 1984-01-17 | Sumitomo Durez Company, Ltd. | Method for accelerating cure of resole type phenolic resins |
| CN1145927A (en) * | 1995-07-12 | 1997-03-26 | 住友电木株式会社 | Phenolic resin molding material |
Also Published As
| Publication number | Publication date |
|---|---|
| HK1026666A1 (en) | 2000-12-22 |
| CN1259424A (en) | 2000-07-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3693733B2 (en) | Phenol novolac mixtures for use with refractory aggregates and methods of making them | |
| CN1173018C (en) | Coal briquette having superior strength and briquetting method thereof | |
| CN1131136C (en) | Mfg. method of phenolic resin shaping material containing little or no free ammonia | |
| JP3911614B2 (en) | Biomass resin composition, method for producing the same, and molding material comprising the biomass resin composition | |
| CN1703436A (en) | Cold-curing binder and process for producing molding with the same | |
| US4058403A (en) | Refractory compositions | |
| CN1305967C (en) | Biomass resin composition ,its preparation method and completed material for said biomass resin composition | |
| CN1732195A (en) | Method for producing shaped bodies, particularly cores, molds and feeders for use in foundry practice | |
| JP5536384B2 (en) | Process for producing modified phenolic resin, phenolic resin composition, refractory composition, resin-coated sand for molding, molding material, nonwoven fabric, cured product, carbide, activated carbon | |
| JP3152421B2 (en) | Method for producing lignocellulose-phenolic resin and lignocellulose-phenolic resin molded product | |
| JPS5827227B2 (en) | refractory | |
| CA2397006C (en) | Carbon-phenol resin molding compound | |
| CN1249170C (en) | Production method of aminoresin formed material | |
| JP2007246689A (en) | Phenolic resin composition for friction material, and friction material | |
| JPH0791420B2 (en) | Talc-based filler, method for producing the same, and amino resin composition containing the same | |
| JP2005095932A (en) | Phenolic resin composition for shell mold, and resin-coated sand | |
| JP4355981B2 (en) | Phenolic resin molding composition | |
| JP4120517B2 (en) | Wood resin for molding on-vehicle components, its manufacturing method, wood resin material for molding on-vehicle components, and on-vehicle components molded therefrom | |
| CN1266859A (en) | Phenol-amino condensation resin, preparing method, epoxy resin composition, prepreg and laminated board thereof | |
| JP2008238202A (en) | Resin composition for shell mold and resin-coated sand for shell mold | |
| JP2005240026A (en) | Resin composition for molding, and molding material containing the same | |
| JP3362590B2 (en) | Manufacturing method of resol resin molding material | |
| JPH0647481A (en) | Production of resin coated sand grain for shell mold | |
| JPH09176259A (en) | Phenolic resin molding material | |
| JPH05148409A (en) | Phenolic resin molding material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term |
Granted publication date: 20031217 |
|
| CX01 | Expiry of patent term |