Machine Translated by Google

C
U
RUSSIAN FEDERATION (19) (11)
RU 2 694 264(13) C2

2
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(51) IPC
C08L 27/06 (2006.01)
C08K 3/34 (2006.01)
C04B 14/20 (2006.01)
C01B 33/18 (2006.01)
B01J 3/08 (2006.01)

FEDERAL SERVICE FOR

INTELLECTUAL PROPERTY

(12) DESCRIPTION OF THE INVENTION TO THE PATENT

(52) SPK
C08L 27/06 (2018.08); C08K 3/34 (2018.08); C04B 14/20 (2018.08); C01B 33/18 (2018.08); B01J 3/08 (2018.08)

(21)(22) Request: 2017143809, 14.12.2017 (72) Author(s):

TIAN, Weiliang (CN), GE,
(24) Start date of the patent term: 12/14/2017
Zhenhong (CN), CHEN,
Minge (CN), QIN,
Registration date: Shaowei (CN), SHU,
07/11/2019 Zunzhe (CN), YUAN,
Xiulin (CN), LI, Liangming
Priority(s): (30) (CN), LIAN, Qianjin
Convention priority: (CN), BU, Ming (CN), CAO,
14.12.2016 CN 201611151511.9
Pengfei (CN)

(43) Date of publication of requests: 17.06.2019 Bull. No. 17

(73) Patentee(s):
(45) Published: 07/11/2019 Bulletin. No. 20
Tarim University (CN)
Address for correspondence:
(56) List of documents cited in the search report: WO
123242, Moscow, pl. Kudrinskaya, 1, PO Box 35,
2015/050766 A1, 04/09/2015. SU 1648938 A1,
"Mikhailyuk, Sorokolat and partners - patent
05/15/1991. CN 103059369 A, 04/24/2013. US
attorneys"
2012/0045637 A1, 02/23/2012. RU 2474543 C2,
02/10/2013. RU 2010898 C1, 04/15/1994. RU
2506241 C2, 02/10/2014. SU 374339 A1,
03/20/1973.

(54) METHOD FOR PRODUCING PVC PRODUCT USING A HEAT STABILIZER FROM VERMICULITE

(57) Abstract:
The present invention relates to a method for producing a supernatant and a solid, wherein the solid obtained after
a PVC product using the thermal stabilizer vermiculite, which washing is a silica-based heat stabilizer; third stage: the
includes the following steps: first stage:
from pre-treatment of supernatant obtained in the second stage, the pH value of
vermiculite: raw vermiculite is washed and dried, crushed and which is adjusted to 3 using sodium hydroxide solution,
heated by flocculation, red solid iron hydroxide is filtered to
obtain the filtrate, with subsequent high-speed stirring, the
expanded by microwaves to obtain mixed solution of the filtrate, sodium hydroxide and sodium
expanded vermiculite, ready to use; second stage: swollen carbonate is gradually poured into the container , after
462496C
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vermiculite is crushed and placed in a solution

hydrogen peroxide and after heating, stirring and separating,
add dilute acid to bring the pH value to 1, carry out the
heating reaction and carry out centrifugation to obtain after a certain reaction time, centrifugation is carried out to
obtain a solid
substances, while the solid substance is re-
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dispersed in distilled water, and then centrifuged and after repeating
washing 3-5 times, dispersed again in distilled water, then
put it in the reactor and perform the reaction
when heated; after the reaction is completed
the solid obtained by centrifugation is a hydroxide-based heat
stabilizer; fourth stage: a solution ofsilicon
ethyl dioxide-
alcohol is added to the
based thermal stabilizer obtained at the second stage or the
hydroxide-based thermal stabilizer obtained at the third stage, and
after 3-5 times of centrifugal mixing using ultrasound, ethanol is
added, and then
dispersion while stirring using
R
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ultrasound add PVC powder and again
after dispersing by stirring with
using ultrasound, a suspension is obtained, then obtained during
centrifugal separation
solid containing silicon dioxide
or hydroxide, as well as a mixture of PVC is dried and
the result is a homogeneous solid mixture of heat stabilizer and
PVC; fifth stage: a plasticizer is added to the resulting solid mixture
of heat stabilizer and PVC, heated and PVC products are obtained.
The technical result is the creation of a simpler, highly effective,
a non-toxic, low-cost method for producing a PVC product using
vermiculite with a special layered structure as an effective thermal
stabilizer for PVC. 5 salary f-ly, 6 ill., 2 ave.
R
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Machine Translated by Google

C
U
RUSSIAN FEDERATION (19) (11)
RU 2 694 264(13) C2

2
R
(51) Int. Cl.
C08L 27/06 (2006.01)
C08K 3/34 (2006.01)
C04B 14/20 (2006.01)
C01B 33/18 (2006.01)
B01J 3/08 (2006.01)

FEDERAL SERVICE
FOR INTELLECTUAL PROPERTY

(12) ABSTRACT OF INVENTION

(52) CPC
C08L 27/06 (2018.08); C08K 3/34 (2018.08); C04B 14/20 (2018.08); C01B 33/18 (2018.08); B01J 3/08 (2018.08)

(21)(22) Application: 2017143809, 14.12.2017 (72) Inventor(s):

TIAN,Weiliang (CN),
(24) Effective date for property rights:
GE, Zhenhong (CN),
14.12.2017
CHEN, Mingge (CN),
Registration date: QIN, Shaowei (CN),
11.07.2019 SHU, Zunzhe (CN),
YUAN, Xiuling (CN),
Priority: LI, Jiangming (CN),
(30) Convention priority: LIAN, Qianjin (CN),
14.12.2016 CN 201611151511.9
BU, Ming (CN),
CAO, Pengfei (CN)
(43) Application published: 17.06.2019 Bull. ÿ 17

(73) Proprietor(s):
(45) Date of publication: 11.07.2019 Bull. ÿ 20
Tarim University (CN)
Mail address:
123242, Moskva, pl. Kudrinskaya, d. 1, a/ya 35,
"Mikhajlyuk, Sorokolat i partnery - patentnye
poverennye"

(54) PVC PRODUCT PRODUCTION METHOD USING VERMICULITE THERMAL STABILIZER (57) Abstract:
FIELD:
chemistry.
SUBSTANCE: presentinvention relatesto a method of
producing aPVC product using a heatstabilizer from
vermiculite, comprising the following steps: a first step:
pretreatment of vermiculite: raw vermiculite is washed and
dried, milled and bulged with microwaves to produce
expanded vermiculite ready for use; second step: the
expanded vermiculite is ground, placed in a hydrogen
peroxide solution and after heating, stirring and stratification
diluted acid is added to bring the pH value to 1, performing
a heating reaction and performing centrifugation to produce
a supernatant and a solid substance, wherein the solid
substance obtained after washing is a silicon dioxide based
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sodium carbonate are gradually poured into a container,
after a certain reaction time, centrifugation is performed to
obtain a solid substance, wherein the solid substance is
repeatedly dispersed in distilled water, and then
centrifugation is carried out and after washing again 3–5
times again dispersed in distilled water,then placed in
reactor and reaction is carried out while heating; after
completion of reaction solid substance obtained by
centrifugation is a heat stabilizer based on hydroxide;
fourth step:in obtained atsecond stage of heatstabilizer
based on silicon dioxide or obtained at third stage heat
stabilizer based on hydroxide is added solution of ethyl
alcohol and after 3–5 times of centrifugal mixing using

heat stabilizer; third step: supernatant obtained at second
step, pH value of which is adjusted to 3 with sodium
hydroxide solution, heated with flocculation, red solid iron
hydroxide is filtered to obtain filtrate, during subsequent
high-speed stirring mixed filtrate solution, sodium hydroxide
and
ultrasound is added ethanol, and after dispersion while
stirring using ultrasound, PVC powder is added and again
after dispersion with stirring using ultrasound a suspension
is obtained,then obtained during centrifugal separation
solid substance containing silicon dioxide or hydroxide, as
well as PVC mixture is dried and as a

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C
result homogeneoussolid mixture of heatstabilizer and PVC is obtained; fifth step: high-efficient, non-toxic,low-cost method of producing PVC product using

U
a plasticizer is added to the obtained solid mixture of heat stabilizer and PVC, vermiculite of special layered structure as effective heat stabilizer of PVC.

heated and PVC products are obtained.

2
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6 cl, 6 dwg, 2 ex

EFFECT: technical result is creation of simpler,

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RU 2 694 264 C2

In the present invention, the ore mineral is taken as a raw material and used
The feature of the layered structure of vermiculite is that by removing one layer
of alumina octahedron in the middle of two layers of silicon-oxygen tetrahedron, a
layered silicon-oxygen tetrahedron is obtained, and then the alumina octahedron is re-
5 prepared to realize the interlayer separation of vermiculite, and the method for preparing
PVC thermal stabilizer is carried out. Specifically speaking, vermiculite ore is
processed by microwave expansion to produce expanded vermiculite; and then carried
out by stirring and stripping using ions to obtain a nanometer grade vermiculite
tablet. In accordance with the fact that the silicon-oxygen tetrahedron is not soluble in
10 acid, and the aluminous octahedron is easily dissolved in acid, vermiculite is carried out
by acid-soluble separation to obtain solid layered silicon dioxide (silicon-oxygen
tetrahedron). The acidic solution is subjected to fractional precipitation method to remove
iron ions in the solution, and then undergoes rapid nucleation and water washing to
remove salt ions and other impurities, finally the crystal growth is controlled by
15 hydrothermal method to obtain nano-sized layered hydroxide (alumina octahedron). The
resulting silica and hydroxide successfully realized the combination of heat stabilizer with
PVC, overcoming the problem of agglomeration and redispersion

20 nano-sized silica and hydroxide using substitution and solvent dispersion method. The
present invention selects mineral vermiculite, which is the dominant mineral in our
country, as the starting material for preparing PVC heat stabilizer, has the following
advantages: wide
source of raw materials, low cost, simple technology, non-toxic and easy to distribute
25 and apply, etc.; In addition, raw vermiculite has prepared an effective thermal
stabilizer, this has overcome the disadvantages of thermal stabilizers about the existing
high prices or lead toxicity, etc., it has important theoretical and practical significance to
promote the development of high-alloy vermiculite products. Technical field: [0001] The
invention relates to a method for producing a PVC
30 thermal stabilizer from
vermiculite, in particular to a method for producing a PVC thermal stabilizer, in
particular to a non-toxic thermal stabilizer for a PVC pipe.

BACKGROUND
35 OF THE INVENTION: [0002] Polyvinyl chloride (PVC) resin is one of the five general
purpose plastics (PEPE, PPPP, PVC, PS, ABS), and is a widely used thermoplastic. PVC
with high mechanical strength, low cost, good chemical resistance (concentrated
hydrochloric acid, 90% sulfuric acid concentration, 60% nitric acid concentration
and 20% sodium hydroxide concentration), good electrical insulation and difficult to burn
40 (Flame retardant value 40 or more) and other advantages, with stable physical and
chemical properties, insoluble in water, alcohol, gasoline, gas, water vapor leakage
and low, widely used in engineering construction, food packaging, electrical and other
industries quality and soft goods. In the world, PVC polymer ranks third, and its
consumption in China has risen to first place. In 2010, the global demand for PVC will
45 reach 37 million tons; in 2011, China's PVC production capacity will reach 22 million
tons, which ranks first in the world.

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PVC production technology is gradually improving and with the support of the authorities. In recent years, in the context of the global
financial crisis, PVC has been steadily developing. In 2015, with the implementation of national industrial restructuring and the
elimination of backward production capacity, domestic PVC production capacity reached 23.48 million tons/year.
In the world, China's PVC resin industry has reached production capacity, production and consumption are engaged in the first three.
5

[0003] Although PVC has many advantages, it has an Achilles heel, that is, poor thermal stability. The PVC polymer chain
structure contains branch points, double bonds and initiator residues and other instability, which makes the chlorine light molecular
10 chain from molecular chain prolapse when heated to 140°C begins to deteriorate, hydrogen chloride, PVC processing and the
normal molding temperature is about 160- 200°C. When the temperature rises, large amounts of HCl are released and accumulated
in the material. Since HCl has a catalytic effect on the decomposition of PVC, the decomposition rate of PVC is greatly
accelerated. After the isolation of HCl, a large number of colored conjugated double bonds are formed in the molecular chain, and the
color of the product appears Dramatic deepening, the overall experience of white-yellow-brown-brown to black process, physical
15 and mechanical properties of the decline phenomenon, and even carbonization to the point of loss of useful value. Therefore, a heat
stabilizer must be added to the molding processing of PVC compositions. Heat stabilizer - This is the most important tool for processing
PVC. It plays an important role in the PVC industry. Thermal stabilizer industry and PVC industry are interdependent

20

and complementary.
25 [0004] In the 1930s, lead salt appeared and first solved the problem of thermal degradation of PVC, becoming the
earliest heat stabilizer. But with increasing environmental awareness among people, problems of toxicity and serious pollution
have severely limited its use. Currently on the market there are PVC lead stabilizer, calcium zinc stabilizer, tin stabilizer,
barium cadmium salt stabilizer, hydrotalcite stabilizer. Lead salts and barium cadmium salts are inexpensive and have excellent
properties. They occupy an important place in the world market. Lead, barium and cadmium and other heavy metal salts have more
30 serious toxicity problems on the human body and the ecological environment. Developed countries have imposed strict
restrictions on the use of lead-cadmium salts, and China has also begun to ban lead completely since 2003. Currently, the US, Europe
and other developed countries have banned the use of lead and cadmium heat stabilizers. Therefore, when the traditional toxic
heat stabilizer was gradually eliminated, the heat stabilizer industry had a huge impact, and the search for new environmentally
friendly heat stabilizers became the heat stabilizer industry and the entire PVC industry to be solved.
35

40

[0005] The Chinese thermostable industry has many problems, such as

lack of sufficient R&D funding, lack of high-level professionals, scientific research and production from abroad, lack of original
product innovation, less variety, slow pace of environmental protection, product structure is irrational; Small production scale,
45 product quality errors such as non-availability. All of the above has seriously limited the development of the thermal stabilization
industry in China. Currently

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I am already deeply researching PVC heat stabilizer. New preparation of raw

materials will continue. More important is to find a cheap and non-toxic PVC heat
stabilizer, which will become the focus of future research and development [0006] Vermiculite
is one of the non-metallic minerals with good resource prospect and potential
5 benefits in our country, it belongs to the important non-metallic mineral, the chemical formula
of vermiculite is: it is
,

magnesium-containing hydrous aluminosilicate secondary metamorphic mineral with a

10
layered structure, belongs to the layered silicate, it is cheap and easily
available. Vermiculite can withstand high temperatures and is a poor conductor with good
electrical insulation; expanded vermiculite easily becomes water-absorbing and hygroscopic;
it expands at high temperatures and peels off easily. Vermiculite has good interlayer cation
exchange ability, swelling ability, adsorption ability, sound insulation, heat insulation,
15
fire resistance, freezing resistance and other characteristics, and chemical
resistance, insoluble in water, non-toxic, tasteless without side effects, the industry mainly
uses its good adsorption properties and ion exchange properties for wastewater treatment
with heavy metals and organic cations, preparation of antimicrobial materials and insulation
materials, vermiculite filtration agent, cleaning agent and organic vermiculites. [0007]
20
Vermiculite has a layered structure, in the middle of two layers of silicon-oxygen tetrahedron
there is one alumina octahedron. If we can separate the alumina octahedron to realize
the interlayer separation of vermiculite, and improve the utilization. Obtain aluminum
octahedral hydroxide products used in PVC heat stabilizer, the
development of high alloy vermiculite products will have important theoretical
25

and practical significance.

30
SUMMARY OF THE
INVENTION [0008] The purpose of the present invention is to overcome the
disadvantages of the prior art and make full use of the characteristics of vermiculite's own
layered structure to provide vermiculite as a raw material for the production of PVC heat
stabilizer, the prepared material can be used as a PVC heat stabilizer. Another purpose of
35
the present invention is to provide a method for constructing new material by resolution
using inorganic stratiform vermiculite as a matrix, that is, a method of exfoliation
between inorganic stratiform layers of vermiculite. The method has the advantages of
simple, high efficiency, low cost, etc., and is capable of developing new vermiculite
products and
40
carry out industrial application of new vermiculite materials.
[0009] In the present invention, an ore mineral is taken as a raw material, and
the layered structure feature of vermiculite is exploited by removing one
layer of alumina octahedron in the middle of two layers of silicon-oxygen tetrahedron, a
45
layered silicon-oxygen tetrahedron is obtained, and then the alumina octahedron is re-
prepared to realize the interlayer separation of vermiculite, and the method for preparing
PVC heat stabilizer is carried out.
[0010] The invention can be achieved using the following technical solutions:

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[0011] A method for producing a PVC heat stabilizer from vermiculite, comprising:
the following steps:
[0012] First stage: vermiculite pre-treatment: raw vermiculite
washed and dried, crushed and microwave expanded to produce expanded vermiculite (reserve);
5

[0013] Second stage: expanded vermiculite, crushed into hydrogen peroxide solution, heated and stirred purified, then
add dilute acid, adjust the pH value to 1, heat, centrifuge, and obtain the supernatant and solid, the solid is washed, and then
thermal silicon stabilizer ;

10

[0014] Third stage: clere from the second stage, with sodium hydroxide solution to adjust the pH value to 3, heat, through
filtration to remove red solid iron hydroxide to obtain the filtrate, with high speed stirring, the filtrate, sodium hydroxide and mixed
sodium carbonate solution gradually poured into the container at the same time, after the reaction, centrifuged to
obtain a solid, and the solid is redispersed in distilled water, and then centrifuged, washed 3-5 times and then dispersed in distilled
15 water, heated. After the reaction, the solid was isolated by centrifugation, that is, a hydrostatic thermostabilizer;

20 [0015] Fourth stage: thermal stabilizer of silicon dioxide from the second
stage or hydroxide heat stabilizer and added to the ethanol solution, stirred, centrifuged with ultrasound, washed 3-5
times, then added ethanol, after mixing with ultrasonic auxiliary dispersion, adding PVC powder and then mixing and after
ultrasonic dispersion to obtain a suspension, centrifugal separation to obtain a solid mixture of silica or hydroxide and a mixture
of PVC, then after drying to obtain a homogeneous heat stabilizer and a solid mixture of PVC;
25

[0016] Fifth stage: in the stabilizer and PVC solid mixture from the fourth stage,
add plasticizer, heat, and get PVC products. [0017] A further method of the invention is: first stage,
30 crushed vermiculite
to 1~80, microwave power is 500-3000W, expansion time 0.5~30
minutes.
[0018] The further method of the invention is: second stage: disintegrate expanding vermiculite 100 ~ 200,
hydrogen peroxide concentration 3 ~ 30% (mass fraction), desorption and stirring temperature is 30-100°C, time is 0.5-12
35 days; , Dilute acid refers to hydrochloric acid, sulfuric acid, nitric acid, the concentration of dilute acid is 0.01~15% (mass fraction),
adding dilute acids, the reaction temperature is 60-100°C, the reaction time is 0.5~15 hours .

40 [0019] The further method of the invention is: in the third stage, the concentration of sodium hydroxide solution is 0.05-1 mol/
L, the flocculation temperature is 50-180°C, the flocculation time is 0.5 ~ 24 hours, the ratio of sodium hydroxide and sodium
carbonate: 1 : 0.1 ~ 1, concentration of sodium hydroxide and sodium carbonate 0.01 ~ 1 mol/L, stirring speed
2000-6000 rpm, stirring reaction time is 1 ~ 60 minutes, reaction vessel temperature is 100 ~ 200°C , reaction time is
6-48 hours. [0020] A further method of the invention is: in: Fourth stage, silicone
45

heat stabilizer or hydrostatic heat stabilizer: PVC 1~30:100

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(mass ratio).
[0021] A further method of the invention is: c: fifth stage, plasticizers, benzene, dicarboxylic acid, dioctyl ether are added
in an amount of 30 ~ 80% (mass ratio), plasticization temperature 150 ~ 200°C, plasticization time 1-30 minutes [0022] The
technical process for preparing silica-hydroxide thermal stabilizer by interlayer separation of vermiculite is shown in FIG. 1. As can
5 be seen from
Fig. 1, through the present experimental process, two kinds of heat stabilizers can be obtained. In fig. 2 shows that
vermiculite with layered structure can be obtained by expanding brown black vermiculite, and the expansion ratio can reach about
20 times. Fig. 3 shows that the broad and strong peak around 1100cm-1 is the asymmetric and antisymmetrical Si-O-Si
spreading vibration peak, the absorption band around 790cm-1 and 500cm-1 is the symmetrical Si-O-Si spreading vibration
10 peak, such three absorption peaks belong to the typical characteristic absorption peaks of SiO2, indicating that the silica was
prepared from vermiculite. In fig. Figure 4 shows that the absorption peak at 1396 cm-1 is the characteristic peak of CO32-,
indicating that the carbonate layered magnesium aluminum hydroxide was obtained from vermiculite. In fig. 5 and 6
show that the heat stabilizer prepared according to this technical process is very effective in stabilizing PVC.

15

20

[0023] In the present invention, an ore mineral is taken as a raw material, and the layered structure feature of
vermiculite is exploited by removing one
layer of alumina octahedron in the middle of two layers of silicon-oxygen tetrahedron, a layered silicon-oxygen tetrahedron is
25 obtained, and then the alumina octahedron is re-prepared to realize the interlayer separation of vermiculite, and the method for
preparing PVC heat stabilizer is carried out. He has

the following characteristics: Brief

description of graphic materials [0024] FIG. 1 - Experimental
30 Technology Roadmap [0025] FIG. 2 - Raw vermiculite and expanded vermiculite used in
examples 1-2 [0026] FIG. 3 - Silica infrared image obtained in example 1. [0027] FIG. 4 - Hydroxide infrared image obtained
in

Example 1. [0028] FIG. 5 - Diagram of thermal stability of silicon dioxide obtained

35

in example 1 (0 - white, 1 - yellowish, 2 - pale yellow, 3 - yellow; 4 - yellowish brown, 5 - reddish-reddish brown, 6 - reddish
brown, 7 - dark brown, 8 - brown, 9 - dark brown, 10 - black). [0029] FIG. 6 - Diagram of thermal stability of hydroxide
obtained in example 1. (0 - white, 1 - yellowish, 2 - pale yellow, 3 - yellow; 4 - yellowish-
brown, 5 - red-reddish-brown, 6 - reddish-brown , 7 - dark brown, 8 - brown, 9 - dark brown, 10 - black).
40

Description of the invention [0030]

Example 1 [0031] Take
45 5 g of vermiculite crushed to 10, microwave power is
1500W, expansion time 60 seconds to obtain expanded vermiculite. Disintegrate expanding
vermiculite 120, hydrogen peroxide concentration 30%, desorption and stirring temperature is 80°C, time

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is 5 days;, Dilute acid refers to hydrochloric acid, sulfuric acid, nitric acid, the concentration of dilute acid is 0.01%, adjust the pH value
to 1 by adding dilute acids, the reaction temperature is 80°C, the reaction time is 3.5 hours. The supernatant and solid were obtained
by centrifugation, and the solid was washed with silica heat stabilizer. [0032] Clare from the above, with 0.1mol/L sodium hydroxide
solution to adjust the pH value to 3, heat, the reaction temperature is 80°C, through filtration to remove the red
5 solid iron hydroxide to obtain a filtrate, and obtain the Filtrate. In a beaker, the mechanical stirring suspension was adjusted to 4000
rpm, the filtrate was 1:1 and sodium hydroxide and mixed sodium carbonate solution (mass concentration of 0.1 mol/L sodium
hydroxide and 0.05 mol/L sodium carbonate) while same time, gradually poured into a beaker while stirring, the reaction mixture
was stirred for 15 minutes, centrifuged to obtain a solid, redispersed solids into distilled water, and then centrifuged and washed
again 3 times, and finally dispersed in distilled water, converted into reaction kettle, the reaction mixture was heated at 110°C
10 for 24 hours, after completion of the reaction, the solid was isolated by centrifugation, that is, a hydroxide heat stabilizer. [0033] The
above obtained silica or hydroxide is added to

15

20

alcohol solution, ratio 1:5 (volume ratio), ultrasonic assisted mixing is carried out for 20 minutes, and centrifuged. After centrifugal
washing with alcohol three times, alcohol is added for ultrasonic assisted mixing and dispersion, PVC powder is added (PVC: silica or
hydroxide = 100:5 (mass ratio)), and ultrasonic assisted mixing and dispersion is carried out for 25 minutes to obtain a homogeneous
suspension , centrifugal separation obtains solid silica heat stabilizer or hydroxide heat stabilizer and PVC mixture, dried to obtain
25 homogeneous heat stabilizer and solid PVC mixture. [0034] In silicone heat stabilizer or hydrostatic heat stabilizer

30

plasticizers are milked, benzene, dicarboxylic acid, dioctyl ether is added in an amount of 50% (mass ratio), plasticization
temperature is 180°C, plasticization time is 5 minutes, and obtain a PVC sample [0035] PVC samples in a heating oven with a
temperature of 180°C for testing For static thermal aging, carried out once every 10 minutes, in
35 accordance with the GB/T2913-1982 standard, PVC whiteness samples are checked. Contains silicon and hydroxyl heat-resistant
PVC coupons for 300 minutes without aging, without heat stabilizer after 140 minutes aging. [0036] Example 2 [0037] Take 5 g raw
vermiculite, crushed to 20, microwave power

40

is 1200W, expansion time is 60 seconds to get expanded vermiculite. Disperse expanding vermiculite 150 concentration of
hydrogen peroxide 30%, desorption and stirring temperature is 80°C, time is 4 days; Adding 0.1 mol/L hydrochloric acid, adjust the
pH to 1 and then heat at 80°C, reflecting the supernatant and the solid obtained by centrifugation after 3 hours, the solid is
45 washed with heat - silica heat stabilizer.

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[0038] The supernatant obtained from the above, using 0.1 mol/L sodium hydroxide solution to adjust the pH value to 3,
heating and flocculation is carried out at a temperature of 80°C, filtered to remove the red solid iron hydroxide to obtain a filtrate;
mechanical stirring blades are added in the beaker, the stirring speed is adjusted to 4000 rpm, the filtrate is 1:1 and the mixed
solution of sodium hydroxide and (mass concentration of sodium hydroxide 0.1 mol/L and sodium carbonate 0.05 mol/L) at the
5 same time is gradually poured into the beaker with idle stirring, the reaction mixture is stirred for 15 minutes, and then a solid is
obtained by centrifugation; the solid is redispersed in distilled water, centrifuged again, and washed repeatedly three times,
and finally dispersed in distilled water, transferred to the reactor, heating and reaction are carried out at 110°C for 24 hours; After
completion of the reaction, the solid is separated by centrifugation, which is what produces the hydroxide thermal stabilizer.

10

15 [0039] The above obtained silica and hydroxide 1:1 (mass ratio) is added to the alcohol solution, ratio 1:5 (volume ratio),
ultrasonic assisted stirring is carried out for 20 minutes, and centrifuged. After centrifugal washing with alcohol three times, alcohol
is added for ultrasonic assisted mixing and dispersion, PVC powder is added (PVC: silica or hydroxide = 100:5 (mass ratio)),
and ultrasonic assisted mixing and dispersion is carried out for 25 minutes to obtain a homogeneous suspension ,
centrifugal separation obtains solid silica heat stabilizer or hydroxide heat stabilizer and PVC mixture, dried to obtain
20 homogeneous heat stabilizer and solid PVC mixture. [0040] In silicone heat stabilizer or hydrostatic heat stabilizer

25

plasticizers, benzene, dicarboxylic acid are added, dioctyl zphyr is added in an amount of 50% (mass ratio), plasticization
temperature is 180°C, plasticization time is 5 minutes, and obtain a PVC sample [0041] PVC samples in a heating oven with a
temperature of 180°C for testing For static thermal aging, carried out once every 10 minutes, in
30 accordance with the GB/T 2913-1982 standard, white PVC samples are checked. Contains silicon and hydroxyl heat-resistant
PVC coupons for 300 minutes without aging. [0042] The foregoing represents only a preferred embodiment of the present
invention, and it should be noted that some improvements and modifications can be made by simple technicians in the
technical field without departing from the principle of the present invention, and these improvements and modifications are to
be considered
35 within the scope of the present invention. inventions.

40
(57) Claim 1. Method for producing a
PVC product using a heat stabilizer from
vermiculite, characterized in that it includes the following steps:
first stage: pre-treatment of vermiculite: raw vermiculite is washed
45 and dried, crushed and expanded by microwaves to obtain expanded vermiculite (ready for use);

second stage: expanded vermiculite is crushed, placed in a solution of hydrogen peroxide and, after heating, mixing and
separation, diluted

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acid to bring the pH value to 1, a heating reaction is carried out and centrifugation is carried out to obtain a supernatant
and a solid, and the solid obtained after washing is a silica-based heat stabilizer;

5 third stage: the supernatant obtained in the second stage, the pH value of which is
using sodium hydroxide solution is adjusted to 3, heated with flocculation, red solid iron hydroxide is filtered to obtain the
filtrate, followed by high-speed stirring, the mixed solution of the filtrate, sodium hydroxide and sodium carbonate is gradually
poured into the container, after a certain reaction time, centrifugation is carried out to obtain a solid, wherein the solid is re-
dispersed in distilled water, and then centrifuged, and after repeating washing 3-5 times, re-dispersed in distilled water, then
10 placed in a reactor and reacted by heating; after completion of the reaction, the solid obtained by centrifugation is a hydroxide-
based heat stabilizer;

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fourth stage: a solution of ethyl alcohol is added to the silicon dioxide-based thermal stabilizer obtained at the second stage or
the hydroxide-based thermal stabilizer obtained at the third stage, and after 3-5 times centrifugal mixing using ultrasound, ethanol
is added, and after dispersing while mixing using ultrasound, PVC powder is added and again, after dispersing with ultrasonic
20 stirring, a suspension is obtained, then the solid substance containing silicon dioxide or hydroxide obtained during centrifugal
separation, as well as the PVC mixture, is dried and as a result a homogeneous solid mixture of the heat stabilizer and PVC is
obtained;

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fifth stage: the resulting solid mixture of heat stabilizer and PVC is added
plasticizer, heated and PVC products are obtained.
2. The method according to claim 1, characterized in that at the first stage the vermiculite is crushed to 1-80 mesh, the microwave
power is 500-3000 W, the swelling time is 0.5-30 minutes. 3. The method according to claim 1, characterized in that at the second
30 stage, the expanded
vermiculite is crushed to 100-200 mesh, the concentration of hydrogen peroxide is 3-30% (mass fraction), the temperature during
mixing and delamination is 30-100°C, time mixing and stratification is 0.5-12 days; dilute acid is hydrochloric acid, sulfuric acid, nitric
acid, the concentration of dilute acid is 0.01-15% (mass fraction), the reaction temperature when adding dilute acid is 60-100°C,
the reaction time is 0.5- 15 hours. 4. The method according to claim 1, characterized in that at the third stage the
35 concentration of sodium hydroxide solution is 0.05-1 mol/l, the flocculation temperature is 50-180°C, the flocculation time is
0.5-24 hours, the hydroxide ratio sodium and sodium carbonate: 1:0.1-1, the concentration of sodium hydroxide and sodium carbonate
is 0.01-1 mol/l, the stirring speed is 2000-6000 rpm, the stirring time during the reaction is 1-60 minutes; the reaction temperature
in the reactor is 100-200°C, the
reaction time is 6-48 hours. 5. The method according to claim 1, characterized in that at the fourth stage the ratio of the thermal
40 stabilizer based on silicon dioxide or the thermal stabilizer based on hydroxide and PVC is 1-30:100 (ratio by weight).

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6. Method according to claim 1, characterized in that at the fifth stage a plasticizer is added
based on dioctyl phthalate in an amount of 30-80% (mass fraction), plasticization temperature is 150-200 ° C, plasticization
time is 1-30 minutes.

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