CN107746542A - One kind suppresses to produce formaldehydogenic method in acetal resin production or process - Google Patents
One kind suppresses to produce formaldehydogenic method in acetal resin production or process Download PDFInfo
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- CN107746542A CN107746542A CN201710953318.5A CN201710953318A CN107746542A CN 107746542 A CN107746542 A CN 107746542A CN 201710953318 A CN201710953318 A CN 201710953318A CN 107746542 A CN107746542 A CN 107746542A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
- C08K5/24—Derivatives of hydrazine
- C08K5/25—Carboxylic acid hydrazides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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- C—CHEMISTRY; METALLURGY
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- 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
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34922—Melamine; Derivatives thereof
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- 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
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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Abstract
Suppress to produce formaldehydogenic method in acetal resin production or process the present invention relates to one kind, this method is included in the step of adding alkyl hydroxy benzenpropanoic acid hydrazide kind compound in acetal resin production or process.Alkyl hydroxy benzenpropanoic acid hydrazide kind compound is added in the production of polyformaldehyde or molding process, formaldehyde caused by can significantly inhibiting oxidation or thermal decomposition of acetal resin etc. generates, and improves operating environment, product is in extremely low formaldehyde spill-out；Meanwhile resin changes colour caused by it can effectively prevent hydrazide kind compound in extruding processing or molding process, assign resin good processing characteristics.
Description
Technical field
The present invention relates to technical field of polymer materials, more particularly to a kind of suppression acetal resin production or process
The middle formaldehydogenic method of production, further relates to a kind of formaldehyde inhibitor for acetal resin.
Background technology
It is well known that acetal resin is in mechanical performance, fatigue resistance, rub resistance or abrasiveness, chemical resistance and shaping
Property etc. there is excellent performance, therefore, acetal resin has been widely used in various fields, as automobile component, electrically
Or electronic unit, other Precision Machinery Elements, building materials or conduit component, life or cosmetic device, medical device element etc..With
The extension or diversified it is necessary to have higher-quality acetal resin of application, it is formaldehydogenic poly- especially for easily producing
For formaldehyde resin, it is the most to suppress formaldehyde (volatile matter VOCs) to distribute (generation) in production, processing and article application process
Important.
In recent years, volatile aldehyde, there is dysgenic factor to environment or health as formaldehyde, acetaldehyde and methacrylaldehyde are used as
The concern of people is increasingly subject to, while proposes the requirement of higher suppression volatile aldehyde.As acetal resin, due to it
The reason for chemical constitution, is easily in high-temperature oxydation atmosphere, or is decomposed in acid or alkaline environment and form volatile matter formaldehyde,
The presence of formaldehyde can pollute the working environment of component assembly and the application environment of end article, meanwhile, formaldehyde has chemism,
Formic acid is oxidized easily, so as to influence the heat resistance of acetal resin.In addition, when acetal resin is as electrically or electronically portion
During part, formaldehyde can cause hard contact to corrode or cause part to change colour due to the deposition of organic compound, and electric contact occurs
Contact fault.Therefore, for acetal resin, it is most effectively to suppress application of the generation (distributing) of formaldehyde for the resin
To be important.
For stabilized polyoxymethylene, the chemism end in stabilized polyoxymethylene molecular structure is not only wanted, while also to stablize
The backbone portion thermal decomposition of polyformaldehyde in heating process, in fact, it is general using add stabilizer (such as antioxidant and other
Stabilizer) mode realize.
But even if adding these stabilizers, it is also difficult to which the decomposition (or degraded) for completely inhibiting polycondensation aldehyde forms formaldehyde.When
Polyformaldehyde when producing extrusion step or forming step melt-processed the process of product being made, acetal resin by extruder or
The effect of heat or oxygen in machine barrel is molded, by producing formaldehyde on the main chain of its decomposition or the end of insufficient stabilization, so that building ring
Border is caused mold deposit to cause product surface to be deteriorated by formaldehyde pollution, or cause resin mechanical performance reduce and
Resin changes colour.
As the inhibitor for suppressing the aldehydes generation, what is be currently known has urea, amino triazine compound, hydrazides chemical combination
The alkalescence such as thing, polyamide contains nitrogen compound.Meanwhile suppression of the hydrazide compound (particularly carboxylic acid hydrazides) therein to aldehydes
Ability is higher.Such as, the addition in acetal resin is disclosed in Japanese Unexamined Patent Publication 4-345648 and contains monocarboxylic acid hydrazides, dicarboxylic acids
The suppression of hydrazides, polyacrylic acid hydrazides to aldehydes is high to a certain extent, can reduce the formaldehyde odor of resin combination.But
It is that disclosed carboxylic acid hydrazides can not still reach preferable degree for the inhibition level of aldehydes, it is impossible to meet for polyformaldehyde
The higher level requirement that PARA FORMALDEHYDE PRILLS(91,95) suppresses in resin application, meanwhile, disclosed monocarboxylic acid hydrazides, dicarboxylic acids hydrazides, polypropylene
Sour hydrazide compound polyformaldehyde process, application when heat effect or with other materials coexist it is lower may occur overflow or discoloration or
Mouldability deteriorates, so as to cause the quality of product or degraded appearance.
The content of the invention
First purpose of the present invention is the defects of presence for prior art and deficiency, there is provided one kind suppresses polyformaldehyde tree
Formaldehydogenic method is produced in fat production or process, this method, which is included in acetal resin production or process, adds alkane
The step of base hydroxy phenylpropionic acid hydrazide kind compound.
Alkyl hydroxy benzenpropanoic acid hydrazide kind compound has hydrazide structure, and two in the hydrazide structure active hydrogen can be with aldehyde
Carbonyl reacted, hydrazone compounds are formed, and the reaction can be completed voluntarily at normal temperatures without heating, so as to realize to poly-
The preferable seizure for the aldehyde for degrading out in formaldehyde, realize the low formaldehyde volatilization of polyformaldehyde.Meanwhile alkyl hydroxy benzenpropanoic acid hydrazides class
Contain alkyl phenolic hydroxyl group in compound structure, be the main functional group for playing thermo oxidative aging degraded, have for polyformaldehyde anti-
Oxidation susceptibility.Two kinds of functional groups of hydrazides and alkyl phenolic hydroxyl group each play a role, and can play thermo oxidative aging and reduce formaldehyde and wave
The double effects of hair.Importantly, alkyl hydroxy benzenpropanoic acid hydrazide kind compound catches the product after formaldehyde, in polyformaldehyde
Equally there is antioxidant effect, while there is good compatibility with acetal resin, processing characteristics, mechanicalness to resin
The improvement such as energy, outward appearance are beneficial, rather than are deterioration as other formaldehyde catching agents.
Preferably, the addition of the alkyl hydroxy benzenpropanoic acid hydrazide kind compound is the 0.3% of acetal resin weight
~0.5%.It is added according to the ratio, can excellently reaches extremely low formaldehyde volatile quantity VOCs purpose.More additions
Amount is uneconomic, meanwhile, such compound is added too much, can not only produce stronger formaldehyde catching effect, Er Qiehui
Cause acetal resin the processing characteristics, mechanical performance etc. the problem of.
When producing acetal resin, preferably after formaldehyde completes polymerisation, end-blocking adds the alkyl hydroxyl before being granulated
Base benzenpropanoic acid hydrazide kind compound.Such a addition manner can build the production environment of low formaldehyde volatile quantity, and contribute to rear
The stable protection of continuous acetal resin application.
When processing acetal resin into product, preferably the alkyl hydroxyl is added before acetal resin carries out heat fusing extrusion
Base benzenpropanoic acid hydrazide kind compound.Such a addition manner can play extremely low formaldehyde volatile quantity in polyformaldehyde processing and product application
Stable protective effect.
It is pointed out that during production acetal resin, the addition of alkyl hydroxy benzenpropanoic acid hydrazide kind compound will be slightly
Higher than processing acetal resin, because being that acetal resin produces formaldehydogenic important step in the production process that end-blocking is granulated.
The method of production acetal resin can use method well known in the art, such as extrude autofrettage, in extrusion, by institute
State alkyl hydroxy benzenpropanoic acid hydrazide kind compound to be fed intake by the side dog-house of extruder, control the melting mixing time in extruder
For short time, such as 10-150s；It is 180-220 DEG C (preferably 200 DEG C) to control extrusion temperature.
Processing acetal resin can equally use method well known in the art into product, such as melt molding processing method, directly
Add after the alkyl hydroxy benzenpropanoic acid hydrazide kind compound of the present invention is mixed with other additives (such as antioxidant, stabilizer etc.)
Enter, into melting mixing.
Inventor has found, when the alkyl hydroxy benzenpropanoic acid hydrazide kind compound is 3,5- di-t-butyl -4- hydroxy benzenes third
Hydrazides, or, for the group of 3,5- di-t-butyl -4- hydroxy benzenes propionyl hydrazines and double (3,5- di-t-butyl -4- hydroxy benzenes propionyl) hydrazines
Compound, there is optimal formaldehyde inhibition.
3,5- di-t-butyl -4- hydroxy benzenes propionyl hydrazines (Formulas I) and double (3,5- di-t-butyl -4- hydroxy benzenes propionyl) hydrazine (formulas
II structure) is as follows：
When only adding compound of formula I, its addition is the 0.3%~0.5% of acetal resin weight.
As adding type I and the mixture of Formula II compound, the addition of the two, which will be less than, is used alone compound of formula I,
More economically, preferable addition is the 0.2-0.4% of acetal resin weight.
As adding type I and the mixture of Formula II compound, compound of formula I has for formaldehyde caused by polyformaldehyde catches
The effect of catching, and Formula II compound has chelating function for metal ion, in polyformaldehyde hot procedure, can effectively suppress gold
The thermo-oxidative ageing for belonging to ion for resin is degraded, and so as to fundamentally suppress formaldehyde generating source, both compoundings are to suppressing formaldehyde
Generation or distribute with synergistic effect.
Preferably, the weight ratio of Formulas I and Formula II compound is 1：When (0.1-0.2), effect is most preferable.
Preferably, the step of method of the invention also includes adding thermo oxidative aging stabilizer, the heat resistanceheat resistant oxygen is old
Change stabilizer and be selected from least one of antioxidant, acid binding agent, lubricant.
Thermo oxidative aging stabilizer is added in acetal resin production or process, polyformaldehyde can be suppressed because of hot oxygen
Caused by degraded so as to stabilized polyoxymethylene.Wherein, antioxidant, acid binding agent, lubricant can use material well known in the art.
Such as, antioxidant can use Hinered phenols product, and lubricant can use amide-type product, acid binding agent can use inorganic compound or
Melamine class compound etc..
Preferably, the antioxidant is selected from double [β-(the 3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) of triethylene-glycol
Propionic ester], hexylene glycol it is double [3- (3,5- di-tert-butyl-hydroxy phenyl) propionic ester], N, N'- be double-(3- (3,5- di-t-butyls-
4- hydroxy phenyls) propiono) hexamethylene diamine, in four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters extremely
Few one kind.It is further preferred that the addition of the antioxidant is the 0.3%~0.5% of acetal resin weight.
Preferably, the acid binding agent is selected from least one of melamine, magnesium hydroxide.It is it is further preferred that described
The addition of acid binding agent is the 0.08%~0.18% of acetal resin weight.
Preferably, lubricant is ethylene bis stearic acid amide.It is further preferred that the addition of the lubricant is poly- first
The 0.1%~0.2% of urea formaldehyde weight.
It will be understood by those skilled in the art that it can also further add other on the basis of thermo oxidative aging stabilizer
Function additive is to assign product other characteristics.Light stabilizer can such as be added to lift the weatherability of polyformaldehyde.Light stabilizer can be adopted
With the benzotriazole ultraviolet absorbent well known in the art with synergistic effect and the composition of HALS class light stabilizers.
Benzotriazole Ultraviolet Stabilizer may be selected from light stabilizer UV-234, UV-326, UV-328, UV-329, UV-360 etc..HALS
Class light stabilizer may be selected from UV-622, UV-944, UV-770 etc..It is stable depending on the application requirement of polyformaldehyde, benzotriazole light
The addition of agent is 0.15-0.30% (relative to weight resin wt%)；The addition of HALS class light stabilizers is 0.20-
0.40% (relative to weight resin wt%).
For another example, in order to improve the polyformaldehyde end properties of the present invention, can also be added in acetal resin a kind of or more
The conventional additive of kind, such as impact modifier (such as esters of acrylic acid core-shell polymer), gloss controlling agent, slide modifier (such as
Selected from olefin polymer, organic siliconresin etc.), releasing agent, nucleator, antistatic agent, fire retardant etc.；Can also be by conventional fibre
Tie up shape filler (such as inorfil glass fibre, organic fiber), granular filler (such as calcium carbonate, talcum powder, carborundum
Deng).
Second object of the present invention is to provide a kind of formaldehyde inhibitor for acetal resin, by weight, bag
Include 0.20-0.50 parts 3,5- di-t-butyl -4- hydroxy benzenes propionyl hydrazines, 0.30-0.50 part antioxidants, 0.08-0.18 parts tie up acid
Agent, 0.10-0.20 part lubricants.
Preferably, by weight, the formaldehyde inhibitor includes 0.15-0.40 parts 3,5- di-t-butyl -4- hydroxy benzenes
The compound of propionyl hydrazine and double (3,5- di-t-butyl -4- hydroxy benzenes propionyl) hydrazines, 0.30-0.50 part antioxidants, 0.08-0.18
Part acid binding agent, 0.10-0.20 part lubricants；
In the compound, 3,5- di-t-butyl -4- hydroxy benzenes propionyl hydrazines and double (3,5- di-t-butyl -4- hydroxy benzenes third
Acyl) hydrazine weight ratio be 1：(0.1-0.2).
Preferably, the antioxidant is selected from double [β-(the 3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) of triethylene-glycol
Propionic ester], hexylene glycol it is double [3- (3,5- di-tert-butyl-hydroxy phenyl) propionic ester], N, N'- be double-(3- (3,5- di-t-butyls-
4- hydroxy phenyls) propiono) hexamethylene diamine, in four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters extremely
Few one kind.
Preferably, the acid binding agent is selected from least one of magnesium hydroxide, melamine.
Preferably, the lubricant is ethylene bis stearic acid amide.
It will be understood by those skilled in the art that other function additives can also be added into the formaldehyde inhibitor, such as may be used
Light stabilizer is added to lift the weatherability of polyformaldehyde.Light stabilizer can use the benzo well known in the art with synergistic effect
The composition of triazole ultra-violet absorber and HALS class light stabilizers.It is steady that Benzotriazole Ultraviolet Stabilizer may be selected from light
Determine agent UV-234, UV-326, UV-328, UV-329, UV-360 etc..HALS class light stabilizers may be selected from UV-622, UV-944,
UV-770 etc..Depending on the application requirement of polyformaldehyde, the addition of benzotriazole light stabilizer for 0.15-0.30% (relative to
Weight resin wt%)；The addition of HALS class light stabilizers is 0.20-0.40% (relative to weight resin wt%).
For another example, in order to improve the polyformaldehyde end properties of the present invention, one kind can also be added in the formaldehyde inhibitor
Or a variety of conventional additives, such as impact modifier (such as esters of acrylic acid core-shell polymer), gloss controlling agent, slide modifier
(such as selected from olefin polymer, organic siliconresin), releasing agent, nucleator, antistatic agent, fire retardant etc.；It will can also commonly use
Fibrous filler (such as inorfil glass fibre, organic fiber), granular filler (such as calcium carbonate, talcum powder, carbon
SiClx etc.).
The formaldehyde inhibitor of the present invention is auxiliary agent bag, can produce in acetal resin and directly be added in process, be made
With conveniently.
The alkyl hydroxy benzenpropanoic acid hydrazide kind compound that the present invention adds has formaldehyde catching and oxidation resistant dual-use function concurrently,
And can be compatible with other auxiliary agents, antagonism will not be produced.Meanwhile such as antioxidant can be reduced to a certain extent and ties up acid
The dosage of agent, more economically.
It on the basis of common sense in the field is met, above-mentioned each optimum condition, can be mutually combined, it is each preferably to produce the present invention
Example.
The present invention relates to the commercially available acquisition of raw material and reagent.
The present invention achieves following good effect：Alkyl hydroxy benzene is added in the production of polyformaldehyde or molding process
Propionic acid hydrazide kind compound (especially Formulas I, Formula II compound), can significantly inhibit oxidation or thermal decomposition of acetal resin etc.
Caused formaldehyde generation, improves operating environment, product is in extremely low formaldehyde spill-out；Meanwhile in extrusion processing or processing and forming
During can effectively prevent hydrazide kind compound caused by resin change colour, assign product good processing characteristics.
Embodiment
Following examples are used to illustrate the present invention, but are not limited to the scope of the present invention.The operation being related in embodiment
Unless otherwise specified, it is this area customary technical operation.
The melt index (MI) of acetal resin copolymer A used in embodiment and comparative example is 9g/10min.Polyformaldehyde
Resin copolymer B melt index (MI) is 26g/10min.
Compound I is 3,5- di-t-butyl -4- hydroxy benzenes propionyl hydrazines；Compound II is double (3,5- di-t-butyl -4- hydroxyls
Phenylpropyl alcohol acyl) hydrazine.
a-1：Antioxidant 245；a-2：Antioxidant 259；a-3：Antioxidant 1098；a-4：Antioxidant 1010；a-5：
(weight is than 1 for antioxidant 245+ antioxidant 1010s:1)；a-6：(weight is than 2 for antioxidant 245+ antioxidants 1098:1)
f-1：Melamine；f-2：Magnesium hydroxide.
r-1：EBS is ethylene bis stearic acid amide.
Embodiment 1
One kind suppresses to produce formaldehydogenic method in acetal resin production process, comprises the following steps：
(1) by 100kg acetal resin A and 0.2kg compounds I, 0.4kg antioxidant 245,0.12kg melamines,
0.15kg ethylene bis stearic acid amides premix is uniform；
(2) mixture of step (1) is put into one has vaccum exhaust outletDouble screw extruder
Dog-house, melting mixing extrusion is carried out, controls the extrusion condition to be：L/D=35,200 DEG C of extrusion temperature, screw rod revolution 100rpm,
Purging vacuum degree 93.1kPa, basic crack 15kg/hr, mean residence time 95s, produces graininess acetal resin.
Embodiment 2-16
Embodiment 2-16 method is differed only in and given birth to according to the material and inventory of Tables 1 and 2 with embodiment 1
Production.
Embodiment 17
One kind suppresses to produce formaldehydogenic method in acetal resin production process, comprises the following steps：
(1) by 90kg acetal resin B and 0.3kg compounds I, 0.45kg antioxidant 245,0.10kg melamines,
0.20kg ethylene bis stearic acid amides premix is uniform；
(2) mixture of step (1) is put into one has vaccum exhaust outletDouble screw extruder
Dog-house, melting mixing extrusion is carried out, controls the extrusion condition to be：L/D=35,200 DEG C of extrusion temperature, screw rod revolution 100rpm,
Purging vacuum degree 93.1kPa, basic crack 15kg/hr, mean residence time 100s, produces graininess acetal resin.
Embodiment 18-23
Embodiment 18-23 method is differed only in and produced according to the material and inventory of table 3 with embodiment 1.
Embodiment 24
A kind of formaldehyde inhibitor for polyformaldehyde, by 0.4kg compounds I, 0.4kg antioxidant 245,0.12kg melamines
Amine, 0.15kg ethylene bis stearic acid amides mix.
Embodiment 25
A kind of formaldehyde inhibitor for polyformaldehyde, by 0.136kg compounds I, 0.014kg compound II, 0.4kg antioxygen
Agent 245,0.12kg melamines, 0.15kg ethylene bis stearic acid amides mix.
Comparative example 1-11
Comparative example 1-11 method is differed only in and produced according to the material and inventory of table 4 with embodiment 1.It is real
It is kg to apply unit of weight in example and comparative example.
Table 1：Embodiment 1-9 feed intake and dosage
Table 2：Embodiment 10-16 feed intake and dosage
Table 3：Embodiment 17-23 feed intake and dosage
Table 4：Comparative example 1-11 feed intake and dosage
Measure of merit
(1) processing stability (appearance color of product)
Using injection moulding machine, the grain forming that embodiment and comparative example are prepared is 100mm × 40mm × 2mm's
Product, observe by visual observation, the appearance color of product is evaluated.
(2) formaldehyde yield of the products formed under wet type environment and exudative
By 4 tabular test film (100mm × 40mm × 2mm；Monolithic surface accumulates 85.6cm2) hang over and distilled containing 50ml
It is under the lid of the ground glass stoppered bottle (volume 1000ml) of water and closed, 3hr is placed in the Water Tank with Temp.-controlled of temperature 60 C, then in room
Temperature is lower to place 1hr, and fully shaking quantifies according to GB/T 7490 to the formaldehyde amount in the aqueous solution, obtains products formed unit
Formaldehyde yield (the μ g/cm of area2)。
The surface state of viewing test rear plate shape experiment slice products formed again, according to following Standard Judgement exudate situation.
○：Have no and ooze out completely；△：It can be seen that ooze out a little；╳：It can be seen that significantly ooze out
(3) formaldehyde yield of the products formed under dry type environment
By 10 experiment slices (50mm × 2mm × 2mm, monolithic total surface area about 40cm2) resin-like piece load closed appearance
It is completely closed in device (volume 20ml).24hr is placed under 80 DEG C of constant temperature of temperature, room temperature is then naturally cooling to, uses syringe
5ml water is injected into the closed container, fully shaking, the formaldehyde amount in the aqueous solution is quantified according to GB/T 7490, asked
Go out formaldehyde yield (the μ g/cm of products formed unit area2)。
Test result is as shown in table 1-4.From table 1-4：
(1) compared with comparative example, the poly- first of chemical compounds I or the compound of chemical compounds I and compound ii is added in embodiment
Urea formaldehyde has lower formaldehyde yield.
(2) chemical compounds I and compound ii have compounding synergistic, and formaldehyde yield is few, therefore, can greatly improve operation
And use environment, the application field requirement of the low formaldehyde spill-out of polyformaldehyde (low VOCs) can be met.
(3) in the case of using chemical compounds I or the compound of chemical compounds I and compound ii, the processing characteristics of polyformaldehyde
Excellent, the products appearance for processing to obtain is white, does not produce yellowing problems.It is visible in wet method formaldehyde produces experiment, use
Its product surface is smooth in the case of the compound of chemical compounds I or chemical compounds I and double compound iis, and nothing oozes out problem.
Although above the present invention is made to retouch in detail with general explanation, embodiment and experiment
State, but on the basis of the present invention, it can be made some modifications or improvements, this is apparent to those skilled in the art
's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, are belonged to claimed
Scope.
Claims (10)
1. one kind suppresses to produce formaldehydogenic method in acetal resin production or process, it is characterised in that：It is included in poly- first
The step of alkyl hydroxy benzenpropanoic acid hydrazide kind compound being added in urea formaldehyde production or process.
2. according to the method for claim 1, it is characterised in that：The addition of the alkyl hydroxy benzenpropanoic acid hydrazide kind compound
Measure as the 0.3%~0.5% of acetal resin weight.
3. method according to claim 1 or 2, it is characterised in that：When producing acetal resin, it is anti-to complete polymerization in formaldehyde
Ying Hou, end-blocking add the alkyl hydroxy benzenpropanoic acid hydrazide kind compound before being granulated；
When processing acetal resin into product, the alkyl hydroxy benzenpropanoic acid is added before acetal resin carries out heat fusing extrusion
Hydrazide kind compound.
4. according to the method described in claim any one of 1-3, it is characterised in that：The alkyl hydroxy benzenpropanoic acid hydrazides class chemical combination
Thing is 3,5- di-t-butyl -4- hydroxy benzenes propionyl hydrazines, or,
The composition of 3,5- di-t-butyl -4- hydroxy benzenes propionyl hydrazines and double (3,5- di-t-butyl -4- hydroxy benzenes propionyl) hydrazines.
5. according to the method for claim 4, it is characterised in that：3,5- di-t-butyl -4- hydroxy benzenes propionyl hydrazines and double (3,5-
Di-t-butyl -4- hydroxy benzenes propionyl) hydrazine weight ratio be 1：(0.1-0.2).
6. according to the method for claim 5, it is characterised in that：3,5- di-t-butyl -4- hydroxy benzenes propionyl hydrazines and double (3,5-
Di-t-butyl -4- hydroxy benzenes propionyl) hydrazine addition be acetal resin weight 0.2-0.4%.
7. according to the method described in claim any one of 1-6, it is characterised in that：Also include adding thermo oxidative aging stabilizer
Step, the thermo oxidative aging stabilizer are selected from least one of antioxidant, acid binding agent, lubricant；
Preferably,
The addition of the antioxidant is the 0.3%~0.5% of acetal resin weight；And/or
The addition of the acid binding agent is the 0.08%~0.18% of acetal resin weight；And/or
The addition of the lubricant is the 0.1%~0.2% of acetal resin weight.
A kind of 8. formaldehyde inhibitor for acetal resin, it is characterised in that：By weight, including 0.20-0.50 parts 3,
5- di-t-butyl -4- hydroxy benzenes propionyl hydrazines, 0.30-0.50 part antioxidants, 0.08-0.18 part acid binding agents, 0.10-0.20 parts profit
Lubrication prescription.
9. formaldehyde inhibitor according to claim 8, it is characterised in that：By weight, including 0.15-0.40 parts 3,5-
The compound of di-t-butyl -4- hydroxy benzenes propionyl hydrazines and double (3,5- di-t-butyl -4- hydroxy benzenes propionyl) hydrazines, 0.30-0.50 parts
Antioxidant, 0.08-0.18 parts acid binding agent/formaldehyde catching agent or acid binding agent, 0.10-0.20 part lubricants；
In the compound, 3,5- di-t-butyl -4- hydroxy benzenes propionyl hydrazines and double (3,5- di-t-butyl -4- hydroxy benzenes propionyl) hydrazines
Weight ratio be 1：(0.1-0.2).
10. formaldehyde inhibitor according to claim 8 or claim 9, it is characterised in that：The antioxidant is selected from two three second two of contracting
Double [3- (3,5- di-t-butyl -4- the hydroxy benzenes of alcohol double [β-(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionic ester], hexylene glycol
Base) propionic ester], N, N'- couples-(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine, four [β-(3,5- bis- tertiary fourths
At least one of base -4- hydroxy phenyls) propionic acid] pentaerythritol ester；And/or
The acid binding agent is selected from least one of melamine, magnesium hydroxide；And/or
The lubricant is ethylene bis stearic acid amide.
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| CN201710953318.5A CN107746542A (en) | 2017-10-13 | 2017-10-13 | One kind suppresses to produce formaldehydogenic method in acetal resin production or process |
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| CN201710953318.5A CN107746542A (en) | 2017-10-13 | 2017-10-13 | One kind suppresses to produce formaldehydogenic method in acetal resin production or process |
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