CN113105157A

CN113105157A - Flame-retardant stone paper and manufacturing method thereof

Info

Publication number: CN113105157A
Application number: CN202110226493.0A
Authority: CN
Inventors: 朱涛; 曲丽娜; 张静; 李红燕
Original assignee: Jinan Luxin New Building Material Co ltd
Current assignee: Jinan Luxin New Building Material Co ltd
Priority date: 2021-03-02
Filing date: 2021-03-02
Publication date: 2021-07-13
Anticipated expiration: 2041-03-02
Also published as: CN113105157B

Abstract

The invention discloses flame-retardant stone paper which comprises the following raw materials in parts by weight: 65-70 parts of calcium carbonate powder, 5-10 parts of superfine slag powder, 15-20 parts of low-density polyethylene, 3-5 parts of modified chlorinated polyethylene, 3-5 parts of sodium dodecyl sulfate, 1-3 parts of a coupling agent, 0-3 parts of a flame retardant, 1 part of DOP, 1 part of zinc stearate, 10101 parts of an antioxidant, 1 part of polyethylene wax and 0-1 part of polyvinyl alcohol. The modified chlorinated polyethylene is porous chlorinated polyethylene obtained by a Soxhlet extraction method, and can contain nano calcium carbonate so as to dilute the calcium carbonate and reduce the flame retardant effect. The chlorinated polyethylene in the invention has the addition amount less than 4% of the total mass, thus having good flame retardant effect and reducing the harm of halogen during combustion. The stone paper disclosed by the invention is high in oxygen index and good in flame retardant property; the mechanical strength and folding endurance are also high. Can be widely used in various flame-retardant occasions.

Description

Flame-retardant stone paper and manufacturing method thereof

Technical Field

The invention relates to the technical field of stone paper, in particular to flame-retardant stone paper and a manufacturing method thereof.

Background

Stone paper is not plant fiber (wood pulp) paper in the traditional sense, nor film plastic (synthetic) paper. The stone paper is modern environment-friendly paper which is prepared by mixing, extruding and forming by using abundant mineral resources in earth crust and high molecular polymers (mainly polyolefin) as main raw materials and adding a plurality of auxiliary raw materials and utilizing a high molecular filling modification technology. It has inherited the advantage of synthetic paper to innovated 3R principle (Reduce, Reuse, Recycle) of having realized, practice thrift promptly, Reuse, the recycling principle, this is paper industry's a change, and neotype environment-friendly stone paper makes the carton after the cardboard that stone paper made, will have the advantage that traditional cardboard does not have: high compression strength, moisture resistance, water resistance, corrosion resistance, no decolorization, etc.

Although the stone paper has excellent performances in all aspects, the filler has a certain dilution and flame retardant function, 20-30% of organic polymer (mostly polyolefin) is added, the melting point and the oxygen index of the organic polymer are very low, particularly the polyolefin, the melting point is only 100-180 ℃, the oxygen index is 17-18, and the stone paper is very easy to ignite to cause fire. The oxygen index of the stone paper is very low, so that the stone paper is extremely easy to burn, thick smoke and molten drops are generated during burning, and the fireproof safety is poor. In order to use the stone paper safely and environmentally, and meet the living needs of people, the fireproof and flame retardant properties of the stone paper are urgently needed to be improved.

Disclosure of Invention

In view of the prior art, the invention aims to provide flame-retardant stone paper. The invention can improve the oxygen index, the mechanical property and the folding times of the stone paper on the premise of not increasing the dosage of the flame retardant. The production cost of the flame-retardant stone paper is reduced, and the flame-retardant stone paper is suitable for wide application.

In order to achieve the purpose, the invention adopts the following technical scheme:

the invention provides flame-retardant stone paper, which comprises the following raw materials in parts by weight:

65-70 parts of calcium carbonate powder, 5-10 parts of superfine slag powder, 15-20 parts of low-density polyethylene, 3-5 parts of modified chlorinated polyethylene, 3-5 parts of sodium dodecyl sulfate, 1-3 parts of a coupling agent, 0-3 parts of a flame retardant, 1 part of DOP, 1 part of zinc stearate, 10101 parts of an antioxidant, 1 part of polyethylene wax and 0-1 part of polyvinyl alcohol.

Preferably, the calcium carbonate powder comprises the following raw materials in particle size: 15-20 parts of particles with the particle size of 60-80 nm and 50 parts of particles with the particle size of 1-10 mu m; the particle size of the superfine slag powder is 1-13 mu m.

Preferably, the modified chlorinated polyethylene is prepared by the following method:

(1) respectively drying polylactic acid and chlorinated polyethylene; mixing the dried polylactic acid and the dried chlorinated polyethylene, and cooling to room temperature;

(2) melting and tabletting the cooled mixture to prepare a film;

(3) and (3) extracting the film obtained in the step (2) by a Soxhlet extraction method, extracting polylactic acid, and drying the film after extraction is finished to obtain the modified chlorinated polyethylene.

More preferably, in the step (1), the mass ratio of the polylactic acid to the chlorinated polyethylene is 1: (1-2); the mixing temperature is 170-200 ℃, and the mixing time is 5-10 min.

More preferably, in the step (2), the melt tabletting is performed by hot pressing at 170-200 ℃ for 1-3 min and then quenching.

More preferably, in step (3), the method further comprises: the extraction temperature of the Soxhlet extraction is 40-150 ℃, and the extraction time is 6-12 hours.

Preferably, the coupling agent comprises an aluminate ester and a-172; the mass ratio of the components is (5-10) to 1.

Preferably, the flame retardant is selected from one or more of a phosphorus-based flame retardant, a nitrogen-based flame retardant and an inorganic flame retardant.

More preferably, the phosphorus flame retardant is triphenyl phosphate, the nitrogen flame retardant is McA, and the inorganic flame retardant is selected from antimony oxide, magnesium hydroxide or aluminum hydroxide.

In a second aspect of the invention, a preparation method of the flame-retardant stone paper is provided, which comprises the following steps:

(1) weighing each raw material and drying;

(2) adding 1/4-1/3 of the total mass of aluminate into calcium carbonate powder with the particle size of 60-80 nm and modified chlorinated polyethylene, adding the calcium carbonate powder and the modified chlorinated polyethylene into an internal mixer, and carrying out densification, and then carrying out densification to obtain a mixture;

(3) and (3) mixing the mixture obtained in the step (2) with other raw materials, mixing and molding to obtain the flame-retardant stone paper.

Preferably, in the step (1), the densification temperature is 190-200 ℃ and the time is 5-10 min; the mixing temperature is 160-180 ℃, and the mixing time is 20-30 min.

Preferably, in the step (2), the mixing temperature is 160-180 ℃, and the mixing time is 20-30 min.

Preferably, in the step (2), the forming method is calendering or tape casting.

The invention has the beneficial effects that:

(1) according to the flame-retardant stone paper disclosed by the invention, the modified Chlorinated Polyethylene (CPE) is added, so that the using amount of a flame retardant can be effectively reduced, and the cost of the flame-retardant stone paper is reduced. Meanwhile, the porous CPE is obtained through modification, so that the nano calcium carbonate can be embedded into the porous CPE, and the dilution of the calcium carbonate to flame retardance is reduced.

(2) According to the application of the stone paper, different flame retardants can be selected or used in a matched manner to achieve different flame retardant grades.

(3) The stone paper disclosed by the invention is high in oxygen index and good in flame retardant property; the mechanical strength and folding endurance are also high. Can be widely used in various flame-retardant occasions. Can also be used as paper for packaging and decoration; express delivery carton boxes; handbag, label paper, etc. The printing effect is good, and the paper surface is level and smooth, non-deformable.

Detailed Description

It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.

As introduced in the background art, the melting point and the oxygen index of the organic polymer in the stone paper are very low, particularly polyolefin, the melting point is only 100-180 ℃, the oxygen index is 17-18, and the stone paper is very easy to ignite and causes fire. And the stone paper contains a large amount of calcium carbonate powder, so that the flame retardant effect of the stone paper is further diluted.

Based on the above, the invention aims to provide the flame-retardant stone paper, which comprises the following raw materials in parts by weight:

The oxygen index of the polyethylene is low, generally between 17 and 18, and the combustion grade of the polyethylene is HB; and the content of calcium carbonate in the general stone paper is more than 65 percent, so that the flame retardance of the stone paper is further diluted. Therefore, a large amount of flame retardant is required to be increased, and if the halogen-free flame retardant is added, the dosage of the halogen-free flame retardant is more than 50-60% to achieve the flame retardant effect. Greatly increased the cost of stone paper, in order to reduce the quantity of fire retardant in the stone paper, a small amount of CPE is added to this application to carry out modification treatment to it. Although the CPE contains halogen, the oxygen index of the CPE is extremely high, generally between 45 and 49, and the combustion grade of the CPE is very high. Can form halogen-antimony synergistic effect with antimony oxide in the flame retardant to carry out high-efficiency flame retardance. However, halogen elements can release harmful substances during combustion, so that the halogen elements cause harm to human bodies and the environment, but the inventor finds that the flame retardance, the mechanical property and the folding resistance of the stone paper can be improved by adding CPE. Therefore, the dosage of the CPE needs to be controlled, so that the dosage of the CPE is controlled within 4%, the halogen content in the stone paper is extremely low, and the harm of the stone paper can be ignored.

In addition, in order to reduce the dilution of calcium carbonate to the flame retardancy of the stone paper, the inventor modifies CPE, blends the modified CPE with polylactic acid, and obtains porous CPE through Soxhlet extraction. The porous CPE is blended with calcium carbonate powder with the particle size of 60-80 nm, so that the calcium carbonate powder is embedded into the porous CPE, and the calcium carbonate powder embedded into the porous CPE is protected by utilizing the high flame retardance of the CPE, so that the dilution of the part of the calcium carbonate powder on the flame retardance of the stone paper can be reduced to the minimum or even ignored.

In addition, the addition of the aluminate coupling agent can improve the hydrophilicity of the calcium carbonate powder and the superfine slag powder, so that the calcium carbonate powder and the superfine slag powder are converted into hydrophobicity, and the printing ink on the stone paper in the later period is favorably printed. The polyvinyl alcohol can be used as a binder of calcium carbonate and superfine slag powder, and the defects of poor smoothness and smoothness, easy deformation and the like of the stone paper are improved. The slag powder is a melt which is obtained by smelting pig iron in a blast furnace in an iron works and takes calcium aluminosilicate as a main component, the cost is low, polyvinyl alcohol can not be added, and the slag powder is used as a binder to improve the compactness of the stone paper. The flame retardant can be compounded according to the flame retardant grade of the stone paper, and besides halogen-antimony synergistic flame retardance, a phosphorus flame retardant triphenyl phosphate can be added as the flame retardant. On occasions with lower requirements on flame retardant grade, inorganic flame retardants such as magnesium hydroxide and aluminum hydroxide can be added; or various flame retardants are compounded for use.

In order to make the technical solutions of the present application more clearly understood by those skilled in the art, the technical solutions of the present application will be described in detail below with reference to specific embodiments.

The test materials used in the examples of the present invention are all conventional in the art and commercially available.

Example 1: preparation of modified chlorinated polyethylene

Respectively drying 15kg of polylactic acid and 15kg of chlorinated polyethylene in a vacuum drying oven at the temperature of 80 ℃ for 1-2 h; and sequentially adding the dried polylactic acid and the dried chlorinated polyethylene into a double-screw extruder, melting and mixing at 190 ℃ for 10min, discharging, and cooling to normal temperature. Then transferring the mixture after melting and mixing into a hot press with the temperature of 190 ℃ for hot pressing for 3min, and then quenching to form a film with the thickness of 50 mu m. And then, extracting the film by a Soxhlet extraction method, wherein an extracting solution is dichloromethane, the Soxhlet extraction temperature is 150 ℃, the extraction time is 6 hours, and after the extraction is finished, taking out the film and naturally airing the film to obtain the porous modified chlorinated polyethylene film.

Example 2

(1) Weighing the raw materials, and drying until the water content is not reduced;

(2) adding 0.6kg of aluminate into 17.5kg of calcium carbonate powder with the particle size of 60-80 nm and 4kg of the modified chlorinated polyethylene prepared in the example 1, adding the mixture into an internal mixer for densification, wherein the densification temperature is 190 ℃ and the time is 6min, and after the densification is finished, putting the mixture into a double-roll open mill for kneading, the kneading temperature is 170 ℃ and the kneading time is 30min, so as to obtain a mixture.

(3) Mixing the mixture with 50kg of calcium carbonate powder with the particle size of 1-10 mu m, 7.5kg of superfine slag powder and 17.5kg of low-density polyethylene in a double-roll open mill for 3min, then adding 4kg of sodium dodecyl sulfate, 1.2kg of aluminate, 0.2kg of A-172, 2kg of antimony oxide, 1kg of DOP, 1kg of zinc stearate, 1kg of antioxidant 1010, 1kg of polyethylene wax and 1kg of polyvinyl alcohol, and mixing at the temperature of 170 ℃ for 25 min. And (5) after the mixing is finished, adjusting the roller spacing to enable the thickness of the stone paper to be 0.2 mm.

Example 3

(2) adding 0.3kg of aluminate into 15kg of calcium carbonate powder with the particle size of 60-80 nm and 3kg of the modified chlorinated polyethylene prepared in the example 1, adding the mixture into an internal mixer for milling, wherein the milling temperature is 190 ℃ and the milling time is 6min, and after the milling is finished, putting the mixture into a double-roll open mill for milling, wherein the milling temperature is 180 ℃ and the milling time is 25min, so as to obtain a mixture.

(3) Mixing the mixture with 50kg of calcium carbonate powder with the particle size of 1-10 mu m, 10kg of superfine slag powder and 20kg of low-density polyethylene in a double-roll open mill for 3min, and then adding 5kg of sodium dodecyl sulfate, 0.6kg of aluminate, 0.1kgA-172, 3kg of triphenyl phosphate, 1kg of DOP, 1kg of zinc stearate, 1kg of antioxidant 1010 and 1kg of polyethylene wax. The mixing temperature is 170 ℃ and the mixing time is 30 min. And (5) after the mixing is finished, adjusting the roller spacing to enable the thickness of the stone paper to be 0.2 mm.

Example 4

(2) adding 0.9kg of aluminate into 20kg of calcium carbonate powder with the particle size of 60-80 nm and 5kg of modified chlorinated polyethylene prepared in the example 1, adding the mixture into an internal mixer for kneading, wherein the kneading temperature is 190 ℃ and the kneading time is 6min, and after the kneading is finished, putting the mixture into a double-roll open mill for kneading, wherein the kneading temperature is 190 ℃ and the kneading time is 20min, so as to obtain a mixture.

(3) Mixing the mixture with 50kg of calcium carbonate powder with the particle size of 1-10 mu m, 5kg of superfine slag powder and 15kg of low-density polyethylene in a double-roll open mill for 3min, and then adding 3kg of sodium dodecyl sulfate, 1.8kg of aluminate, 0.3kgA-172, 1kg of McA, 1kg of DOP, 1kg of zinc stearate, 1kg of antioxidant 1010, 1kg of polyethylene wax and 1kg of polyvinyl alcohol. The mixing temperature is 180 ℃ and the mixing time is 20 min. And (5) after the mixing is finished, adjusting the roller spacing to enable the thickness of the stone paper to be 0.2 mm.

Examples 5 to 10

Examples 5 to 10 the raw materials and preparation methods were the same as in example 2, except that the type and amount of the flame retardant were different. The types and amounts of the flame retardants used in the different examples are shown in Table 1.

TABLE 1 flame retardants

Test example performance characterization:

the stone papers prepared in examples 2 to 4 and 11 were tested for tensile strength, tear strength and simple folding endurance (an average of three times per test). The results are shown in Table 2. Wherein:

the tensile strength was measured in accordance with GB/T1040.3-2006 using an electronic universal tester, and the specimen size was 150 mm. times.20 mm. times.0.2 mm, and the tensile rate was 10 mm/min.

The tear strength was measured using an electronic universal tester according to GBffl6578.1-2008, and the sample size was 150mm × 50mm × 0.2mm, and the tensile rate was 20 mm/mm.

The simple folding endurance test method for determining the folding endurance of the reference paper and the paperboard comprises the steps of folding a stone paper sample once, repeatedly folding the sample along the folding line, and recording the folding times when the sample is broken, wherein the folding endurance is higher, and the folding endurance of the stone paper is also higher. The sample size was 50 mm. times.50 mm. times.0.2 mm.

TABLE 2

Item	Example 2	Example 3	Example 4	Example 11
					Tensile strength MPa	11.2	10.8	11.5	10.6
Tear strength MPa	5.5	5.2	5.6	5.1
					Degree of folding resistance	＞1000	＞1000	＞1000	＞1000

The rich mineral papers prepared in examples 2 to 11 were tested for oxygen index and vertical burning rating (averaged three times for each test) and the results are shown in Table 3.

Wherein: limited oxygen index test A JF.3 type oxygen index tester is used for testing according to GB/T2406.2-2009, the size of a sample is 140mm multiplied by 52mm multiplied by 0.2mm, and the purity of the used nitrogen and oxygen in the experiment is 99.9%.

UL.94 vertical burning rating test Using a CZF.6 type horizontal vertical burning tester in accordance with GB/T2408-2008, a test specimen having a length of 125mm and a width of 13mm was obtained by pressing stone paper of examples 2 to-10 into a thickness of 1.6mm using a two-roll mill and then cutting the stone paper.

TABLE 3

Item	Oxygen index value	Vertical combustion class
			Example 2	32.0	V0
Example 3	31.4	V0
			Example 4	30.6	V0
Example 5	30.1	V0
			Example 6	31.5	V0
Example 7	31.3	V0
			Example 8	30.7	V0
Example 9	29.9	V0
			Example 10	28.0	V0
Example 11	27.2	V0

As can be seen from Table 2, the stone paper of the present invention has very high tensile strength and tear strength, since CPE is a chlorinated polyethylene polymer, and the addition of halogen groups can improve the mechanical strength of polyethylene. Meanwhile, the addition of various auxiliary materials improves the folding resistance of the stone paper.

As can be seen from Table 3, the maximum limiting oxygen index of the stone paper prepared in example 2 is mainly due to the synergistic effect of halogen-antimony which improves the flame retardancy of the stone paper. In addition, as can be seen from example 11, in the case of not adding the flame retardant, since CPE has excellent flame retardancy and the effect of diluting the flame retardant with calcium carbonate is reduced, even if the flame retardant is not added, the flame retardant effect is still good. The stone paper has the flame retardant grade of V0 grade, can be applied to various flame retardant occasions below V0 grade, and can be selected to use a flame retardant or not added with the flame retardant according to the cost requirement and the like. The flame retardant effect is good.

In addition, the stone paper prepared by the invention has good compactness, smoothness, flatness and attractive appearance.

The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. The flame-retardant stone paper is characterized by comprising the following raw materials in parts by weight:

2. The flame-retardant stone paper as claimed in claim 1, wherein the calcium carbonate powder comprises the following raw materials in particle size: 15-20 parts of particles with the particle size of 60-80 nm and 50 parts of particles with the particle size of 1-10 mu m; the particle size of the superfine slag powder is 1-13 mu m.

3. The flame retardant stone paper as claimed in claim 1, wherein the modified chlorinated polyethylene is prepared by the following method:

(2) melting and tabletting the cooled mixture to prepare a film;

4. The flame-retardant stone paper as claimed in claim 3, wherein in the step (1), the mass ratio of the polylactic acid to the chlorinated polyethylene is 1: (1-2); the mixing temperature is 170-200 ℃, and the mixing time is 5-10 min.

5. The flame-retardant stone paper as claimed in claim 3, wherein in the step (2), the melt-pressed sheet is subjected to hot pressing at 170-200 ℃ for 1-3 min and then subjected to rotary quenching.

6. The flame-retardant stone paper as claimed in claim 3, wherein in step (3): the extraction temperature of the Soxhlet extraction is 40-150 ℃, and the extraction time is 6-12 hours.

7. The fire retardant stone paper as recited in claim 1, wherein the coupling agent comprises aluminate ester and a-172; the mass ratio of the components is (5-10) to 1.

8. The flame-retardant stone paper as claimed in claim 1, wherein the flame retardant is selected from one or more of phosphorus flame retardant, nitrogen flame retardant and inorganic flame retardant.

9. The preparation method of the flame-retardant stone paper as claimed in any one of claims 1 to 8, characterized by comprising the following steps:

(1) weighing each raw material and drying;

10. The method according to claim 9, wherein the densification temperature is 190 to 200 ℃ for 5 to 10 min; the mixing temperature is 160-180 ℃, and the mixing time is 20-30 min.