CN1276372A - Trioxane storage method, polyformaldehyde resin obtained by polymerization thereof and producing process thereof - Google Patents

Abstract

A preservation method of trioxane is characterized by adding specifically suffocating amine compound based compound of formula to trioxane.

Description

Trioxane storage method, the polyformaldehyde resin and the production method thereof that obtain by its polymerization

Trioxane is the tripolymer of formaldehyde, and its fusing point is 64 ℃.This is a kind of important material, mainly as the raw material of yuban or multipolymer, also is used for various Industrial products.The ， trioxane from the raw material Formaldehyde Production, wherein will use catalyzer such as sulfuric acid, resin cation (R.C.), zeolite with generally well-known method on technical scale.The present invention relates to store the method for trioxane, and relate to the trioxane composition.

Therefore trioxane is unsettled to oxygen sensitive.Particularly, when molten state is stored, even because the ， trioxane that exists of a small amount of oxygen also can be oxidized, thereby increase its formic acid content greatly, and even its formaldehyde content.In addition, know that the symphysis of generating unit segregation becomes polyoxymethylene owing to wherein have small amount of impurities when cooling of fused trioxane and curing.Moreover, when containing a small amount of sulphur compound in the trioxane, polymerization also can take place owing to the existence of this sulphur compound generate polyoxymethylene, described sulphur compound is to derive as the sulfuric acid of synthetic catalyst when producing trioxane.

Clear, when the trioxane that contains such small amount of impurities as the raw material of polyacetal copolymer, and when polymerization taking place generating multipolymer, this impurity is not little to the negative impact of polyreaction, thus the also quality of the polymkeric substance produced of influence.

Therefore, people have proposed the method for various storage trioxanes.For example, JP-B-54-43514 proposes to add in the Zai trioxane organic trivalent phosphorous compound.JP-B-55-12025 proposes to add in the Zai trioxane thiocarbamyl compound (employed " JP-B " is meant the Japanese patent gazette of " examining ") here.JP-A-7-242652 proposes at cyclic formals, be to add a kind of hindered amine in known a kind of production polyacetal copolymer raw material (copolymerization) monomer, its objective is to prevent cyclic formals rotten (used " JP-A " is meant the Japanese patent gazette of " not examination ") here.

Yet; a kind of organic trivalent phosphorous compound like this or thiocarbamyl compound; though for preventing that forming polyoxymethylene in cooling and solidified trioxane is effectively, be invalid in the time of in joining trioxane for the formation that suppresses formic acid and formaldehyde.

On the other hand, when phenolic antioxidant such as hindered phenol etc. joins in the trioxane separately, for preventing that the increase of formic acid and formaldehyde may be effective in the trioxane.Yet in this case, the polyoxymethylene that forms in the cooling curing process of fusion trioxane can be settled out white floss when fusion again, and this floss can stick on the inwall of pipeline and melt basin, makes its obstruction; Perhaps, when containing a small amount of sulphur compound in the trioxane, will generate polyoxymethylene owing to the effect generation polymerization of this sulphur compound, the polyoxymethylene that forms can blocking pipe and miscellaneous equipment like this.Therefore, owing to these reasons, adding such oxidation inhibitor can produce some negative impacts to the safe handling of device.

An object of the present invention is to provide and a kind ofly under good condition, store trioxane, the method for fusion trioxane especially, and a kind of package stability De trioxane composition that has is provided.

The present invention is a kind of method of storing trioxane, it is characterized in that adding in the Zai trioxane a kind of hindered amine compound shown in the general formula (I):

In the formula:

R ₁Represent hydrogen atom or contain the organic residue of 1 valency of 1-30 carbon atom;

R ₂To R ₅Each representative contains the alkyl of 1-5 carbon atom, and they can be identical or different;

N represents 1 or bigger integer;

R ₆Represent 1 organic residue of n valency.

The present invention also is a kind of hindered amine compound De trioxane composition that contains trioxane and general formula (I): In the formula:

R ₁Represent hydrogen atom or contain the organic residue of 1 valency of 1-30 carbon atom;

R ₂To R ₅Each representative contains the alkyl of 1-5 carbon atom, and they can be identical or different;

N represents 1 or bigger integer;

R ₆Represent 1 organic residue of n valency.

Describe the present invention below in detail.

Can be used for hindered amine of the present invention and comprise, for example following compounds: [1]

????No.	????n	????R	????No.	????n	????R
						????A-1	????0	????H	????E-1	????4	????H
????A-2	????0	????Me	????E-2	????4	????Me
						????B-1	????1	????H	????F-1	????6	????H
????B-2	????1	????Me	????F-2	????6	????Me
						????C-1	????2	????H	????G-1	????8	????H
????C-2	????2	????Me	????G-2	????8	????Me
						????D-1	????3	????H	????H-1	????10	????H
????D-2	????3	????Me	????H-2	????10	????Me

[2]

????No.	????n	????R	????No.	????n	????R
						????I-1	????0	????H	????L-1	????6	????H
????I-2	????0	????Me	????L-2	????6	????Me
						????J-1	????1	????H	????M-1	????8	????H
????J-2	????1	????Me	????M-2	????8	????Me
						????K-1	????4	????H	????N-1	????10	????H
????K-2	????4	????Me	????N-2	????10	????Me

[3]

????No.	Orientation	????R
			????P-1	The o-orientation	????H
????P-2	The o-orientation	????Me
			????Q-1	The m-orientation	????H
????Q-2	The m-orientation	????Me
			????R-1	The p-orientation	????H
????R-2	The p-orientation	????Me

[4]

????No.	????R
		????S-1	????H
????S-2	????Me

[5]

????No.	????R
		????T-1	????H
????T-2	????Me

[6]

????No.	????R
		????U-1	????H
????U-2	????Me

[7]

????No.	????R
		????V-1	????H
????V-2	????Me

[8]

????No.	????R
		????W-1	????H
????W-2	????Me

[9]

????No.	????R
		????X-1	????H
????X-2	????Me

[10]

????No.	????R
		????Y-1	????H
????Y-2	????Me

In these hindered amine compounds, particularly preferably be sebacic acid two (1,2,2,6,6-pentamethyl--4-piperidyl) ester and sebacic acid two (2,2,6,6-tetramethyl--4-piperidyl) ester is because these two kinds of compounds are for the increase that prevents formic acid and formaldehyde in the trioxane and prevent to form the effective of formaldehyde in the solidification process of fusion trioxane.

In the present invention, for the Shi trioxane can be stored 5 days or the longer time under good condition, and make the De trioxane of storing also can under good condition, carry out polymerization, usually, for trioxane, the add-on of hindered amine is preferably 0.5～50ppm, more preferably 1～20ppm.

Hindered amine compound can join in the trioxane as it is, still, in order to promote itself Yu the mixing of trioxane, the solution of this compound in organic solvent can be joined in the trioxane.Organic solvent comprises, for example, and aromatic hydrocarbons such as benzene, toluene and dimethylbenzene, aliphatic hydrocrbon such as normal hexane, normal heptane and hexanaphthene, alcohols such as methyl alcohol and ethanol, halohydrocarbon such as chloroform, methylene dichloride and 1,2-ethylene dichloride, and ketone such as acetone and methylethylketone.

The hindered amine compound that uses among the present invention also can work effectively for containing sulphur compound De trioxane.

In the present invention, hindered phenol compound can join in the trioxane with hindered amine compound, so that further block the formation of formic acid in the trioxane.This class hindered phenol compound comprises, for example, triethylene glycol two (3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl) propionic ester), 1, (3-(3 for 6-hexylene glycol two, the 5-di-tert-butyl-hydroxy phenyl) propionic ester), (3-(3 for tetramethylolmethane four, the 5-di-tert-butyl-hydroxy phenyl) propionic ester), (3-(3 for octadecyl, the 5-di-tert-butyl-hydroxy phenyl) propionic ester), N, N-hexa-methylene two (3,5-di-t-butyl-4-hydroxyl-hydroxylation cinnamide), 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid ester, 3-(3, the 5-di-tert-butyl-hydroxy phenyl) the different monooctyl ester of propionic acid etc.Particularly preferably be triethylene glycol two (3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl) propionic ester) and 1,6-hexylene glycol two (3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester).

For the Shi trioxane can be stored 5 days or the longer time under good condition, and make the De trioxane of storing also can under good condition, carry out polymerization, usually, for trioxane, the add-on of hindered phenol compound is preferably 0.5～500ppm, more preferably 1～100ppm.

Storing the De trioxane according to the inventive method can directly carry out polymerization in the presence of catalyzer such as boron trifluoride or its title complex, obtain the higher high quality polymethanal polymer of productive rate.

Specifically, the mixture that makes according to the method described above the trioxane composition stored and cyclic ethers boron trifluoride catalyst based in the presence of carry out mass polymerization, adding catalyst deactivation agent in the resulting reaction mixture is then perhaps washed catalyzer off.After this operation steps, reaction mixture is heated under the temperature that is not less than the multipolymer fusing point to remove unsettled end group, so just obtain polyacetal copolymer.

As the catalyst deactivation agent that will join in the reaction mixture that contains multipolymer, preferably aminated compounds, especially hindered amine compound.Hindered amine compound can join in the reaction mixture same as before, but in order to strengthen the effect that it stops polyreaction, the solution of this compound in organic solvent can be joined in the reaction mixture.This class organic solvent comprises, for example, and aromatic hydrocarbons such as benzene, toluene and dimethylbenzene, aliphatic hydrocrbon such as normal hexane, normal heptane and hexanaphthene, alcohols such as methyl alcohol and ethanol, halohydrocarbon such as chloroform, methylene dichloride and 1,2-ethylene dichloride, and ketone such as acetone and methylethylketone.

The amount of the amine compound that adds better is such: the number of nitrogen-atoms is equal to or greater than the number that is used for the catalyst based boron atom of polymeric boron trifluoride in the feasible amine compound that is added.Yet even when the number of nitrogen-atoms during less than the number of boron atom, this amine compound still can demonstrate the effect that it makes catalyst deactivation.But in this case, the thermostability of polymkeric substance can be hanged down to a certain extent.Therefore, the amount of the amine compound that add must suitably be controlled according to the desired degree of thermostability to the polymkeric substance that will obtain.

Removing catalyzer from reaction mixture can realize with any currently known methods.For example, water or the organic solvent that contains basic cpd can be joined in the reaction mixture, so that catalyst deactivation, then by the polyacetal copolymer in the filtered and recycled mixture.This class basic cpd comprises, for example basic metal or alkaline earth metal hydroxides, inorganic weak acid salt, organic acid salt etc.Aminated compounds such as ammonia, triethylamine, Tributylamine etc. also are operable.

If desired, can in the polyacetal copolymer of producing according to the inventive method, add any additives, for example, filler, fibrous toughener, uv-absorbing agent, die lubricant, nucleator, softening agent, tinting material, adhesion promotor and other additive be not as long as these additives can influence effect of the present invention.

Illustrate in greater detail the present invention below with reference to following example and comparative example, still, these examples are not to be used for limiting the scope of the invention.In these examples, prepared sample is analyzed, according to formic acid content and the formaldehyde content in the following method mensuration trioxane, and measure polymkeric substance pyrolytic degree.

Formic acid content:

In order to measure the formic acid content of trioxane, trioxane is joined in the acetone solvent that is added with 0.01N NaOH, so that neutralization titration.Use automatic potentiometer to measure.

Formaldehyde content:

The Dui trioxane carries out gas chromatographic analysis to measure its formaldehyde content.For this reason, use the GC-14B of the Shimadzu company that has the TSR-1 chromatographic column, column temperature is 100 ℃, and used carrier gas is a helium.

Pyrolysis degree (Kx):

Kx represents that sample is in the degree of pyrolysis of X ℃ of maintenance after 60 minutes.About 10mg sample is remained in the thermobalance (thermal analyzer of E.I.Du Pont Company, 1090/1091) that X ℃ of air gas encloses to measure its pyrolysis degree.The Kx of sample represents with following formula:

Kx＝(W0-W1)×100/W0(％)

The weight of sample before the W0 representative heating in the formula, the weight of W1 representative heating back sample.

MI (melt index)

The MI of the polymkeric substance of being produced measures according to JIS K 7210 under 190 ℃ and 2160g loading condiction.

Here used additive is as follows:

HA-1: sebacic acid two (1,2,2,6,6-pentamethyl--4-piperidyl) ester

HA-2: sebacic acid two (2,2,6,6-tetramethyl--4-piperidyl) ester

HA-3: trolamine

HP-1: triethylene glycol two (3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl) propionic ester)

HP-2:1,6-hexylene glycol two (3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester)

Example 1:

5.1kg fusion trioxane (containing 3ppm formic acid and 5ppm formaldehyde as impurity, 70 ℃ of temperature) joined to be equipped with to make heat-transfer medium therein in the closed autoclave of round-robin chuck and stirring rake, be added with 5ppm HA-1 in the still.Have air in the autoclave, allow 70 ℃ hot water circulate by chuck, this mixture storage is stored away, the formic acid content after 5 days in the ， trioxane is 7ppm, and formaldehyde content is 8ppm.The content increase that these data show formic acid in the fusion trioxane that is stored in the autoclave and formaldehyde seldom.Then, get 100g trioxane sample, be allowed to condition at 20 ℃ of cooling curings.Place after 2 hours this sample is put into baking oven 70 ℃ of heating, allow sample reheat fusing.Filter and collect polyoxymethylene flocculation white depositions, use the washing with acetone after drying, claim its weight then.This sedimentary amount seldom, its weight is 4.2mg.

Add 172g 1 in the fusion trioxane of in autoclave, storing toward 5.0kg, 3-dioxolane, 3.5g methylal and 6.6g contain the benzole soln of 0.6g boron trifluoride/diethyl etherificate thing, and stir with 40rpm speed, allow 70 ℃ hot water circulate simultaneously by chuck.In about 1.5 minutes, monomer just begins polymerization, and internal temperature rises.Under the internal temperature of about 110 ℃ rising, continue to stir 10 minutes.Formed reaction mixture is ground, obtain the white powder shaped polymer.In polymkeric substance, add the benzole soln that 192g contains 10g sebacic acid two (1,2,2,6,6-pentamethyl--4-piperidyl) ester.Then resulting mixture is placed 10 liters of ribbon mixers to stir 5 minutes to stop polyreaction.Again toward wherein adding 24g triethylene glycol two (3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl) propionic ester) and 4.8g calcium stearate, and stirred 3 minutes.Formed mixture is extruded by the 45mm diameter twin screw extruder that ventilation plant is housed of Ikegai, and wherein the temperature of mixture is 250 ℃, and draft pressure is 5mmHg.Polymer-extruded one-tenth tape is cut into the material grain with dicing machine.The polymer weight that obtains like this is 4.8kg.The productive rate height reaches 92%.Drying is 5 hours in material grain (section) 80 ℃ of air oven.The MI of polymkeric substance is 9.5, and pyrolysis degree K 230 is 2.2%.Polymer quality is good.Data are listed in the table 1.

Example 2:

By the method identical, add 8ppm HA-1 in the Zai trioxane and test with example 1.Formic acid content after 5 days in the ， trioxane is 6ppm, and formaldehyde content is 7ppm.These data show that formic acid and formaldehyde increase are seldom in the trioxane.The amount of formed white depositions is 3.9mg in the 100g trioxane, as seen seldom.The MI of formed polymkeric substance is 9.6, and K230 is 2.0%.The quality of polymkeric substance is good.The productive rate of polymkeric substance is 90.5%, also is high.

Example 3:

By the method identical, add 8ppm HA-2 in the Zai trioxane and test with example 1.Formic acid content after 5 days in the ， trioxane is 7ppm, and formaldehyde content is 9ppm.These data show that formic acid and formaldehyde increase are seldom in the trioxane.The amount of formed white depositions is 4.2mg in the 100g trioxane, as seen seldom.The MI of formed polymkeric substance is 9.9, and K230 is 2.4%.The quality of polymkeric substance is good.The productive rate of polymkeric substance is 90.0%, also is high.

Example 4:

By the method identical, add 8ppm HA-1 in the Zai trioxane and 55ppmHP-1 tests with example 1.Formic acid content after 5 days in the ， trioxane is 5ppm, and formaldehyde content is 6ppm.These data show that formic acid and formaldehyde increase are seldom in the trioxane.The amount of formed white depositions is 5.1mg in the 100g trioxane, as seen seldom.The MI of formed polymkeric substance is 8.8, and K230 is 2.2%.The quality of polymkeric substance is good.The productive rate of polymkeric substance is 91.2%, also is high.

Example 5:

By the method identical, add 8ppm HA-1 in the Zai trioxane and 55ppmHP-2 tests with example 1.Formic acid content after 5 days in the ， trioxane is 6ppm, and formaldehyde content is 6ppm.These data show that formic acid and formaldehyde increase are seldom in the trioxane.The amount of formed white depositions is 5.5mg in the 100g trioxane, as seen seldom.The MI of formed polymkeric substance is 9.0, and K230 is 2.0%.The quality of polymkeric substance is good.The productive rate of polymkeric substance is 90.8%, also is high.

Comparative example 1:

By the method identical, do not add hindered amine compound in the Zai trioxane and hindered phenol compound is tested with example 1.Formic acid content after 5 days in the ， trioxane is 215ppm, and formaldehyde content is 350ppm.These data show that formic acid and formaldehyde increase a lot in the trioxane.The amount of formed white depositions is 56g in the 100g trioxane, and is as seen very big.The MI of formed polymkeric substance is 17.0, and K230 is 20.3%.The poor quality of polymkeric substance.The productive rate of polymkeric substance is 85.1%.

Comparative example 2:

By the method identical, add 55ppm HP-1 in the Zai trioxane and test with example 1.Formic acid content after 5 days in the ， trioxane is 98ppm, and formaldehyde content is 203ppm.These data show that formic acid and formaldehyde increase a lot in the trioxane.The amount of formed white depositions is 43g in the 100g trioxane, and is as seen very big.The MI of formed polymkeric substance is 15.1, and K230 is 28.8%.The poor quality of polymkeric substance.The productive rate of polymkeric substance is 82.4%.

Comparative example 3:

By the method identical, add 55ppm HP-2 in the Zai trioxane and test with example 1.Formic acid content after 5 days in the ， trioxane is 110ppm, and formaldehyde content is 189ppm.These data show that formic acid and formaldehyde increase a lot in the trioxane.The amount of formed white depositions is 49g in the 100g trioxane, and is as seen very big.The MI of formed polymkeric substance is 18.1, and K230 is 29.2%.The poor quality of polymkeric substance.The productive rate of polymkeric substance is 81.1%.

Comparative example 4:

By the method identical, add 5ppm HA-3 in the Zai trioxane and test with example 1.Formic acid content after 5 days in the ， trioxane is 78ppm, and formaldehyde content is 66ppm.These data show that formic acid and formaldehyde increase a lot in the trioxane.The amount of formed white depositions is 32g in the 100g trioxane, and is as seen very big.The MI of formed polymkeric substance is 14.3, and K230 is 19.8%.The poor quality of polymkeric substance.The productive rate of polymkeric substance is 86.0%.Table 1

	Aminated compounds		Hindered phenol		The quality of 5 days Hou trioxanes			Polymer quality		Polymer yield (%)
											Kind	Add-on (ppm)	Kind	Add-on (ppm)	Formic acid content (ppm)	Formaldehyde content (ppm)	Formed white depositions	?????M1 ??(g/10min)	???K230 ???(％)
	Example 1	?HA-1	????5	????-	????-	????7	????8	????4.3mg	????9.5											????2.2	????92.0
Example 2										?HA-1	????8	????-	????-	????6	????7	????3.9mg	????9.6	????2.0	????90.5
	Example 3	?HA-2	????8	????-	????-	????7	????9	????4.2mg	????9.9											????2.4	????91.0
Example 4										?HA-1	????8	??HP-1	????55	????5	????6	????5.1mg	????8.8	????2.0	????91.2
	Example 5	?HA-1	????8	??HP-2	????55	????6	????6	????5.5mg	????9.0											????2.2	????90.8
Comparative example 1										???-	????-	????-	????-	????215	????350	????56g	????17.0	????20.3	????85.1
	Comparative example 2	???-	????-	??HP-1	????55	????98	????203	????43g	????15.1											????28.8	????82.1
Comparative example 3										???-	????-	??HP-2	????55	????110	????89	????49g	????18.1	????29.2	????81.1
	Comparative example 4	??HA-3	????5	????-	????-	????78	????66	????32g	????14.3											????19.8	????86.0

Can obviously find out from above-mentioned data, the superiority of trioxane storage method of the present invention is the formation that prevented formic acid, formaldehyde and white depositions in the De trioxane storing according to the present invention, and stores De trioxane ratio like this and provided high-quality polymkeric substance.

Describe the present invention in detail and with reference to its specific embodiments after, for persons skilled in the art, it should be apparent that, can make various changes and modification to the present invention and can not deviate from its spirit and scope.

Claims (11)

1. method of storing trioxane is characterized in that adding a kind of hindered amine compound shown in the general formula (I) in trioxane: In the formula:

R ₁Represent hydrogen atom or contain the organic residue of 1 valency of 1-30 carbon atom;

R ₂To R ₅Each representative contains the alkyl of 1-5 carbon atom, and they can be identical or different;

N represents 1 or bigger integer;

R ₆Represent 1 organic residue of n valency.

2. as the desired trioxane storage method of claim 1, wherein the amount of the hindered amine compound that will add is 0.5～50ppm for trioxane.

3. as claim 1 or 2 desired trioxane storage methods, wherein the amount of the hindered amine compound that will add is 1～20ppm for trioxane.

4. as any one desired trioxane storage method in the claim 1～3, wherein said hindered amine compound is sebacic acid two (1,2,2,6,6-pentamethyl--4-piperidyl) ester or sebacic acid two (2,2,6,6-tetramethyl--4-piperidyl) ester.

5. as any one desired trioxane storage method in the claim 1～4, wherein further add a kind of hindered phenol compound in the Zai trioxane.

6. as the desired trioxane storage method of claim 5, wherein said hindered phenol compound is triethylene glycol two (3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl) propionic ester) or 1,6-hexylene glycol two (3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester).

7. trioxane composition that contains the hindered amine compound of trioxane and general formula (I): In the formula:

R ₁Represent hydrogen atom or contain the organic residue of 1 valency of 1-30 carbon atom;

R ₂To R ₅Each representative contains the alkyl of 1-5 carbon atom, and they can be identical or different;

N represents 1 or bigger integer;

R ₆Represent 1 organic residue of n valency.

8. as the desired trioxane composition of claim 7, said composition further contains a kind of hindered phenol compound.

9. method of producing copolyoxymethylenes, this method comprises: the mixture that trioxane composition and a kind of cyclic ethers of claim 7 or 8 are formed at least a from by boron trifluoride, boron trifluoride hydrate and contain boron trifluoride and polymerizing catalyst that the organic compound of oxygen or sulphur atom is formed selects one group in the presence of carry out mass polymerization; After the polymerization, in polymerization system, add a kind of catalyst deactivation agent or flush away catalyzer from polymerization system.

10. as the method for the desired production copolyoxymethylenes of claim 9, wherein said catalyst deactivation agent is a kind of hindered amine compound shown in the general formula (I): In the formula:

R ₁Represent hydrogen atom or contain the organic residue of 1 valency of 1-30 carbon atom;

R ₂To R ₅Each representative contains the alkyl of 1-5 carbon atom, and they can be identical or different;

N represents 1 or bigger integer;

R ₆Represent 1 organic residue of n valency.

11. the copolyoxymethylenes of producing according to the method for claim 9 or 10.